Cationic poly alpha-1,3-glucan ethers

ABSTRACT

Poly alpha-1,3-glucan ether compounds are disclosed herein comprising positively charged organic groups. The degree of substitution of the ether compounds is about 0.05 to about 3.0. Also disclosed are methods of producing poly alpha-1,3-glucan ether compounds having positively charged organic groups, as well as methods of using these ether compounds for increasing the viscosity of a aqueous compositions. Hydrocolloids and aqueous solutions comprising the ether compounds are also disclosed.

This application claims the benefit of U.S. Provisional Application No.61/917,507 (filed Dec. 18, 2013) and 62/014,273 (filed Jun. 19, 2014),both of which are incorporated herein by reference in their entireties.

FIELD OF INVENTION

This invention is in the field of poly alpha-1,3-glucan derivatives.Specifically, this invention pertains to cationic poly alpha-1,3-glucanethers and methods of their preparation and use as viscosity modifiers.

BACKGROUND

Driven by a desire to find new structural polysaccharides usingenzymatic syntheses or genetic engineering of microorganisms or planthosts, researchers have discovered polysaccharides that arebiodegradable, and that can be made economically from renewableresource-based feedstocks. One such polysaccharide is polyalpha-1,3-glucan, a glucan polymer characterized by havingalpha-1,3-glycosidic linkages. This polymer has been isolated bycontacting an aqueous solution of sucrose with a glucosyltransferaseenzyme isolated from Streptococcus salivarius (Simpson et al.,Microbiology 141:1451-1460, 1995).

U.S. Pat. No. 7,000,000 disclosed the preparation of a polysaccharidefiber comprising hexose units, wherein at least 50% of the hexose unitswithin the polymer were linked via alpha-1,3-glycosidic linkages usingan S. salivarius gtfJ enzyme. This enzyme utilizes sucrose as asubstrate in a polymerization reaction producing poly alpha-1,3-glucanand fructose as end-products (Simpson et al., 1995). The disclosedpolymer formed a liquid crystalline solution when it was dissolved abovea critical concentration in a solvent or in a mixture comprising asolvent. From this solution continuous, strong, cotton-like fibers,highly suitable for use in textiles, were spun and used.

Kiho et al. (Carb. Res. 189:273-270, 1989) disclosed the alkalineextraction and isolation of poly alpha-1,3-glucan from the fungus,Agrocybe cylindracea, which was further derivatized to sodiumcarboxymethylglucan (CMG). This ether derivative exhibited anti-tumorproperties against sarcoma. Similarly, Zhang et al. (Intl. Publ. No.CN1283633) described the extraction of poly alpha-1,3-glucan from themedicinal fungus, Ganoderma lucidum, and its derivatization to CMG.

SUMMARY OF INVENTION

In one embodiment, the invention concerns a composition comprising apoly alpha-1,3-glucan ether compound represented by the structure:

wherein(i) n is at least 6,(ii) each R is independently an H or a positively charged organic group,and(iii) the compound has a degree of substitution of about 0.05 to about3.0.

In a second embodiment, at least one positively charged organic groupcomprises a substituted ammonium group. This positively charged organicgroup can comprise a trimethylammonium group in a third embodiment. In afourth embodiment, the positively charged organic group can be aquaternary ammonium group.

In a fifth embodiment, at least one positively charged organic groupcomprises an alkyl group or hydroxy alkyl group. The compound in thisembodiment may contain one type of positively charged organic group, ortwo or more types of positively charged organic group. At least onepositively charged organic group can be a quaternary ammoniumhydroxypropyl group, for example.

In a sixth embodiment, the invention concerns a method for producing apoly alpha-1,3-glucan ether compound. This method comprises contactingpoly alpha-1,3-glucan in a reaction under alkaline conditions with atleast one etherification agent comprising a positively charged organicgroup. At least one positively charged organic group is etherified tothe poly alpha-1,3-glucan in this contacting step, thereby producing apoly alpha-1,3-glucan ether compound represented by the structure:

wherein(i) n is at least 6,(ii) each R is independently an H or the positively charged organicgroup, and(iii) the compound has a degree of substitution of about 0.05 to about3.0. A poly alpha-1,3-glucan ether compound produced by this method canoptionally be isolated.

In a seventh embodiment, the alkaline conditions of the reactioncomprise an alkali hydroxide solution.

In an eighth embodiment, the reaction comprises an organic solvent. Theorganic solvent is isopropanol in a ninth embodiment.

In a tenth embodiment, the contacting step of the method furthercomprises heating the reaction, and/or neutralizing the pH of thereaction.

In an eleventh embodiment of the method, at least one positively chargedorganic group comprises a substituted ammonium group. At least onepositively charged organic group comprises a trimethylammonium group ina twelfth embodiment.

In a thirteenth embodiment, the invention concerns a hydrocolloid oraqueous solution comprising a poly alpha-1,3-glucan ether compoundrepresented by the structure:

wherein(i) n is at least 6,(ii) each R is independently an H or a positively charged organic group,(iii) the compound has a degree of substitution of about 0.05 to about3.0, and(iv) the hydrocolloid or aqueous solution has a viscosity of at leastabout 10 cPs.

In a fourteenth embodiment, the invention concerns a method forincreasing the viscosity of an aqueous composition. This methodcomprises contacting a poly alpha-1,3-glucan ether compound as disclosedherein with an aqueous composition, thereby increasing the viscosity ofthe aqueous composition.

In a fifteenth embodiment, the invention concerns a method of treating amaterial. This method comprises contacting a material with an aqueouscomposition comprising a poly alpha-1,3-glucan ether compound asdisclosed herein. The poly alpha-1,3-glucan ether compound adsorbs tothe surface of the material in certain embodiments of this method.

DETAILED DESCRIPTION OF INVENTION

The disclosures of all patent and non-patent literature cited herein areincorporated herein by reference in their entirety.

As used herein, the term “invention” or “disclosed invention” is notmeant to be limiting, but applies generally to any of the inventionsdefined in the claims or described herein. These terms are usedinterchangeably herein.

The terms “poly alpha-1,3-glucan”, “alpha-1,3-glucan polymer” and“glucan polymer” are used interchangeably herein. Poly alpha-1,3-glucanis a polymer comprising glucose monomeric units linked together byglycosidic linkages (i.e., glucosidic linkages), wherein at least about50% of the glycosidic linkages are alpha-1,3-glycosidic linkages. Polyalpha-1,3-glucan is a type of polysaccharide. The structure of polyalpha-1,3-glucan can be illustrated as follows:

Poly alpha-1,3-glucan that can be used for preparing polyalpha-1,3-glucan ether compounds herein can be prepared using chemicalmethods. Alternatively, it can be prepared by extracting it from variousorganisms, such as fungi, that produce poly alpha-1,3-glucan.Alternatively still, poly alpha-1,3-glucan can be enzymatically producedfrom sucrose using one or more glucosyltransferase (gtf) enzymes (e.g.,gtfJ), such as described in U.S. Pat. No. 7,000,000, and U.S. PatentAppl. Publ. Nos. 2013/0244288 and 2013/0244287 (all of which areincorporated herein by reference), for example.

The terms “glucosyltransferase enzyme”, “gtf enzyme”, “gtf enzymecatalyst”, “gtf”, and “glucansucrase” are used interchangeably herein.The activity of a gtf enzyme herein catalyzes the reaction of thesubstrate sucrose to make the products poly alpha-1,3-glucan andfructose. Other products (byproducts) of a gtf reaction can includeglucose (results from when glucose is hydrolyzed from the glucosyl-gtfenzyme intermediate complex), various soluble oligosaccharides (e.g.,DP2-DP7), and leucrose (results from when glucose of the glucosyl-gtfenzyme intermediate complex is linked to fructose). Leucrose is adisaccharide composed of glucose and fructose linked by an alpha-1,5linkage. Wild type forms of glucosyltransferase enzymes generallycontain (in the N-terminal to C-terminal direction) a signal peptide, avariable domain, a catalytic domain, and a glucan-binding domain. A gtfherein is classified under the glycoside hydrolase family 70 (GH70)according to the CAZy (Carbohydrate-Active EnZymes) database (Cantarelet al., Nucleic Acids Res. 37:D233-238, 2009).

The percentage of glycosidic linkages between the glucose monomer unitsof poly alpha-1,3-glucan used to prepare poly alpha-1,3-glucan ethercompounds herein that are alpha-1,3 is at least about 50%, 60%, 70%,80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% (or any integer value between50% and 100%). In such embodiments, accordingly, poly alpha-1,3-glucanhas less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1%, or 0%(or any integer value between 0% and 50%) of glycosidic linkages thatare not alpha-1,3.

Poly alpha-1,3-glucan used to produce poly alpha-1,3-glucan ethercompounds herein is preferably linear/unbranched. In certainembodiments, poly alpha-1,3-glucan has no branch points or less thanabout 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% branch points as apercent of the glycosidic linkages in the polymer. Examples of branchpoints include alpha-1,6 branch points, such as those present in mutanpolymer.

The terms “glycosidic linkage” and “glycosidic bond” are usedinterchangeably herein and refer to the type of covalent bond that joinsa carbohydrate (sugar) molecule to another group such as anothercarbohydrate. The term “alpha-1,3-glycosidic linkage” as used hereinrefers to the type of covalent bond that joins alpha-D-glucose moleculesto each other through carbons 1 and 3 on adjacent alpha-D-glucose rings.This linkage is illustrated in the poly alpha-1,3-glucan structureprovided above. Herein, “alpha-D-glucose” will be referred to as“glucose”.

The terms “poly alpha-1,3-glucan ether compound”, “poly alpha-1,3-glucanether”, and “poly alpha-1,3-glucan ether derivative” are usedinterchangeably herein. A poly alpha-1,3-glucan ether compound hereincan be represented by the structure:

Regarding the formula of this structure, n can be at least 6, and each Rcan independently be a hydrogen atom (H) or a positively charged organicgroup. A poly alpha-1,3-glucan ether compound herein has a degree ofsubstitution of about 0.05 to about 3.0. Given that polyalpha-1,3-glucan ether compounds herein have one or more types ofpositively charged organic groups, these compounds can be considered“cationic”.

A poly alpha-1,3-glucan ether compound is termed an “ether” herein byvirtue of comprising the substructure —C_(G)—O—C—, where “—C_(G)—”represents carbon 2, 4, or 6 of a glucose monomeric unit of a polyalpha-1,3-glucan ether compound, and where “—C—” is comprised in thepositively charged organic group.

Poly alpha-1,3-glucan ether compounds disclosed herein are synthetic,man-made compounds.

A “positively charged organic group” group as used herein refers to achain of one or more carbons (“carbon chain”) that has one or morehydrogens substituted with another atom or functional group (i.e., a“substituted alkyl group”), where one or more of the substitutions iswith a positively charged group. Where a positively charged organicgroup has a substitution in addition to a substitution with a positivelycharged group, such additional substitution may be with one or morehydroxyl groups, oxygen atoms (thereby forming an aldehyde or ketonegroup), alkyl groups, and/or additional positively charged groups. Apositively charged organic group has a net positive charge since itcomprises one or more positively charged groups.

The terms “positively charged group”, “positively charged ionic group”and “cationic group” are used interchangeably herein. A positivelycharged group comprises a cation (a positively charged ion). Examples ofpositively charged groups include substituted ammonium groups,carbocation groups and acyl cation groups.

A composition that is “positively charged” herein typically has moreprotons than electrons and is repelled from other positively chargedsubstances, but attracted to negatively charged substances.

The terms “substituted ammonium group”, “substituted ammonium ion” and“substituted ammonium cation” are used interchangeably herein. Asubstituted ammonium group herein comprises structure I:

R₂, R₃ and R₄ in structure I each independently represent a hydrogenatom or an alkyl, aryl, cycloalkyl, aralkyl, or alkaryl group. Thecarbon atom (C) in structure I is part of the chain of one or morecarbons (“carbon chain”) of the positively charged organic group. Thecarbon atom is either directly ether-linked to a glucose monomer of polyalpha-1,3-glucan, or is part of a chain of two or more carbon atomsether-linked to a glucose monomer of poly alpha-1,3-glucan. The carbonatom in structure I can be —CH₂—, —CH— (where a H is substituted withanother group such as a hydroxy group), or —C— (where both H's aresubstituted).

A substituted ammonium group can be a “primary ammonium group”,“secondary ammonium group”, “tertiary ammonium group”, or “quaternaryammonium” group, depending on the composition of R₂, R₃ and R₄ instructure I. A primary ammonium group herein refers to structure I inwhich each of R₂, R₃ and R₄ is a hydrogen atom (i.e., —C—NH₃ ⁺). Asecondary ammonium group herein refers to structure I in which each ofR₂ and R₃ is a hydrogen atom and R₄ is an alkyl, aryl, or cycloalkylgroup. A tertiary ammonium group herein refers to structure I in whichR₂ is a hydrogen atom and each of R₃ and R₄ is an alkyl, aryl, orcycloalkyl group. A quaternary ammonium group herein refers to structureI in which each of R₂, R₃ and R₄ is an alkyl, aryl, or cycloalkyl group(i.e., none of R₂, R₃ and R₄ is a hydrogen atom).

A quaternary ammonium poly alpha-1,3-glucan ether herein can comprise atrialkyl ammonium group (where each of R₂, R₃ and R₄ is an alkyl group),for example. A trimethylammonium group is an example of a trialkylammonium group, where each of R₂, R₃ and R₄ is a methyl group. It wouldbe understood that a fourth member (i.e., R₁) implied by “quaternary” inthis nomenclature is the chain of one or more carbons of the positivelycharged organic group that is ether-linked to a glucose monomer of polyalpha-1,3-glucan.

An example of a quaternary ammonium poly alpha-1,3-glucan ether compoundis trimethylammonium hydroxypropyl poly alpha-1,3-glucan. The positivelycharged organic group of this ether compound can be represented asstructure II:

where each of R₂, R₃ and R₄ is a methyl group. Structure II is anexample of a quaternary ammonium hydroxypropyl group.

A “hydroxy alkyl” group herein refers to a substituted alkyl group inwhich one or more hydrogen atoms of the alkyl group are substituted witha hydroxyl group. An example of a hydroxy alkyl group is a hydroxypropylgroup; structure II comprises a hydroxypropyl group.

A “halide” herein refers to a compound comprising one or more halogenatoms (e.g., fluorine, chlorine, bromine, iodine). A halide herein canrefer to a compound comprising one or more halide groups such asfluoride, chloride, bromide, or iodide. A halide group may serve as areactive group of an etherification agent.

The terms “reaction”, “reaction composition”, and “etherificationreaction” are used interchangeably herein and refer to a reactioncomprising at least poly alpha-1,3-glucan and an etherification agent.These components are typically dissolved and/or mixed in an aqueousalkali hydroxide. A reaction is placed under suitable conditions (e.g.,time, temperature) for the etherification agent to etherify one or morehydroxyl groups of the glucose units of poly alpha-1,3-glucan with apositively charged organic group, thereby yielding a polyalpha-1,3-glucan ether compound.

The term “alkaline conditions” herein refers to a solution or mixture pHof at least 11 or 12. Alkaline conditions can be prepared by any meansknown in the art, such as by dissolving an alkali hydroxide in asolution or mixture.

The terms “etherification agent” and “alkylation agent” are usedinterchangeably herein. An etherification agent herein refers to anagent that can be used to etherify one or more hydroxyl groups of one ormore glucose units of poly alpha-1,3-glucan with a positively chargedorganic group. An etherification agent thus comprises a positivelycharged organic group.

The term “poly alpha-1,3-glucan slurry” herein refers to an aqueousmixture comprising the components of a glucosyltransferase enzymaticreaction such as poly alpha-1,3-glucan, sucrose, one or moreglucosyltransferase enzymes, glucose and fructose. This composition is aslurry since the poly alpha-1,3-glucan is not dissolved therein.

The term “poly alpha-1,3-glucan wet cake” herein refers to polyalpha-1,3-glucan that has been separated from a slurry and washed withwater or an aqueous solution. Poly alpha-1,3-glucan is not completelydried when preparing a wet cake.

The term “degree of substitution” (DoS) as used herein refers to theaverage number of hydroxyl groups substituted in each monomeric unit(glucose) of a poly alpha-1,3-glucan ether compound. Since there arethree hydroxyl groups in each monomeric unit in poly alpha-1,3-glucan,the degree of substitution in a poly alpha-1,3-glucan ether compoundherein can be no higher than 3.

The term “molar substitution” (M.S.) as used herein refers to the molesof a positively charged organic group per monomeric unit of a polyalpha-1,3-glucan ether compound. Alternatively, M.S. can refer to theaverage moles of etherification agent used to react with each monomericunit in poly alpha-1,3-glucan (M.S. can thus describe the degree ofderivatization of an etherification agent). It is noted that the M.S.value for poly alpha-1,3-glucan may have no upper limit. For example,when a positively charged organic group containing a hydroxyl group(e.g., hydroxyethyl or hydroxypropyl) has been etherified to polyalpha-1,3-glucan, the hydroxyl group of the organic group may undergofurther reaction, thereby coupling more of the positively chargedorganic group to the poly alpha-1,3-glucan.

The term “crosslink” herein refers to a chemical bond, atom, or group ofatoms that connects two adjacent atoms in one or more polymer molecules.It should be understood that, in a composition comprising crosslinkedpoly alpha-1,3-glucan ether, crosslinks can be between at least two polyalpha-1,3-glucan ether molecules (i.e., intermolecular crosslinks);there can also be intramolecular crosslinking. A “crosslinking agent” asused herein is an atom or compound that can create crosslinks.

An “aqueous composition” herein refers to a solution or mixture in whichthe solvent is at least about 20 wt % water, for example, and whichcomprises poly alpha-1,3-glucan and/or a poly alpha-1,3-glucan ethercompound. Examples of aqueous compositions herein are aqueous solutionsand hydrocolloids.

The terms “hydrocolloid” and “hydrogel” are used interchangeably herein.A hydrocolloid refers to a colloid system in which water is thedispersion medium. A “colloid” herein refers to a substance that ismicroscopically dispersed throughout another substance. Therefore, ahydrocolloid herein can also refer to a dispersion, emulsion, mixture,or solution of poly alpha-1,3-glucan and/or one or more polyalpha-1,3-glucan ether compounds in water or aqueous solution.

The term “aqueous solution” herein refers to a solution in which thesolvent is water. Poly alpha-1,3-glucan and/or one or more polyalpha-1,3-glucan ether compounds herein can be dispersed, mixed, and/ordissolved in an aqueous solution. An aqueous solution can serve as thedispersion medium of a hydrocolloid herein.

The terms “dispersant” and “dispersion agent” are used interchangeablyherein to refer to a material that promotes the formation andstabilization of a dispersion of one substance in another. A“dispersion” herein refers to an aqueous composition comprising one ormore particles (e.g., any ingredient of a personal care product,pharmaceutical product, food product, household product, or industrialproduct disclosed herein) that are scattered, or uniformly scattered,throughout the aqueous composition. It is believed that polyalpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds can act asdispersants in aqueous compositions disclosed herein.

The term “viscosity” as used herein refers to the measure of the extentto which a fluid or an aqueous composition such as a hydrocolloidresists a force tending to cause it to flow. Various units of viscositythat can be used herein include centipoise (cPs) and Pascal-second(Pas). A centipoise is one one-hundredth of a poise; one poise is equalto 0.100 kg·m⁻¹·s⁻¹. Thus, the terms “viscosity modifier” and“viscosity-modifying agent” as used herein refer to anything that canalter/modify the viscosity of a fluid or aqueous composition.

The term “shear thinning behavior” as used herein refers to a decreasein the viscosity of the hydrocolloid or aqueous solution as shear rateincreases. The term “shear thickening behavior” as used herein refers toan increase in the viscosity of the hydrocolloid or aqueous solution asshear rate increases. “Shear rate” herein refers to the rate at which aprogressive shearing deformation is applied to the hydrocolloid oraqueous solution. A shearing deformation can be applied rotationally.

The term “contacting” as used herein with respect to methods ofincreasing the viscosity of an aqueous composition refers to any actionthat results in bringing together an aqueous composition with polyalpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compound.Contacting can be performed by any means known in the art, such asdissolving, mixing, shaking, or homogenization, for example.

The terms “fabric”, “textile”, and “cloth” are used interchangeablyherein to refer to a woven material having a network of natural and/orartificial fibers. Such fibers can be thread or yarn, for example.

A “fabric care composition” herein is any composition suitable fortreating fabric in some manner. Examples of such a composition includelaundry detergents and fabric softeners.

The terms “heavy duty detergent” and “all-purpose detergent” are usedinterchangeably herein to refer to a detergent useful for regularwashing of white and colored textiles at any temperature. The terms “lowduty detergent” or “fine fabric detergent” are used interchangeablyherein to refer to a detergent useful for the care of delicate fabricssuch as viscose, wool, silk, microfiber or other fabric requiringspecial care. “Special care” can include conditions of using excesswater, low agitation, and/or no bleach, for example.

An “oral care composition” herein is any composition suitable fortreating an soft or hard surface in the oral cavity such as dental(teeth) and/or gum surfaces.

The term “adsorption” herein refers to the adhesion of a compound (e.g.,poly alpha-1,3-glucan ether) to the surface of a material.

The “molecular weight” of poly alpha-1,3-glucan and polyalpha-1,3-glucan ether compounds herein can be represented asnumber-average molecular weight (M_(n)) or as weight-average molecularweight (M_(w)). Alternatively, molecular weight can be represented asDaltons, grams/mole, DPw (weight average degree of polymerization), orDPn (number average degree of polymerization). Various means are knownin the art for calculating these molecular weight measurements, such ashigh-pressure liquid chromatography (HPLC), size exclusionchromatography (SEC), or gel permeation chromatography (GPC).

The terms “percent by volume”, “volume percent”, “vol %” and “v/v %” areused interchangeably herein. The percent by volume of a solute in asolution can be determined using the formula: [(volume ofsolute)/(volume of solution)]×100%.

The terms “percent by weight”, “weight percentage (wt %)” and“weight-weight percentage (% w/w)” are used interchangeably herein.Percent by weight refers to the percentage of a material on a mass basisas it is comprised in a composition, mixture or solution.

The terms “increased”, “enhanced” and “improved” are usedinterchangeably herein. These terms refer to a greater quantity oractivity such as a quantity or activity slightly greater than theoriginal quantity or activity, or a quantity or activity in large excesscompared to the original quantity or activity, and including allquantities or activities in between. Alternatively, these terms mayrefer to, for example, a quantity or activity that is at least 1%, 2%,3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%,100% 125%, 150%, 175%, or 200% (or any integer between 1% and 200%) morethan the quantity or activity for which the increased quantity oractivity is being compared.

Development of new poly alpha-1,3-glucan ether derivatives and methodsof preparing such derivatives is desirable given their potential utilityin various applications. There is a keen interest in understanding theapplicability of poly alpha-1,3-glucan ether derivatives as viscosityand rheology modifiers of hydrocolloid or aqueous compositions.

Embodiments of the disclosed invention concern a composition comprisinga poly alpha-1,3-glucan ether compound represented by the structure:

Regarding the formula of this structure, n can be at least 6, and each Rcan independently be an H or a positively charged organic group.Furthermore, the poly alpha-1,3-glucan ether compound has a degree ofsubstitution of about 0.05 to about 3.0.

Significantly, a poly alpha-1,3-glucan ether compound of the inventioncan modify the viscosity of an aqueous solution to which it is added.This viscosity modification effect is often coupled with a rheologymodification effect. Furthermore, when contacting a hydrocolloid oraqueous solution herein with a surface (e.g., fabric surface), one ormore poly alpha-1,3-glucan ether compounds adsorb to the surface.

The degree of substitution (DoS) of a poly alpha-1,3-glucan ethercompound disclosed herein can alternatively be about 0.2 to about 2.0.Alternatively still, the DoS can be at least about 0.2, 0.3, 0.4, 0.5,0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9,2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. It would beunderstood by those skilled in the art that since a polyalpha-1,3-glucan ether compound herein has a degree of substitutionbetween about 0.05 to about 3.0, and by virtue of being an ether, the Rgroups of the compound cannot only be hydrogen.

The percentage of glycosidic linkages between the glucose monomer unitsof poly alpha-1,3-glucan ether compounds herein that are alpha-1,3 is atleast about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100%(or any integer between 50% and 100%). In such embodiments, accordingly,the compound has less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%,2%, 1%, or 0% (or any integer value between 0% and 50%) of glycosidiclinkages that are not alpha-1,3.

The backbone of a poly alpha-1,3-glucan ether compound herein ispreferably linear/unbranched. In certain embodiments, the compound hasno branch points or less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%,or 1% branch points as a percent of the glycosidic linkages in thepolymer. Examples of branch points include alpha-1,6 branch points.

The formula of a poly alpha-1,3-glucan ether compound in certainembodiments can have an n value of at least 6. Alternatively, n can havea value of at least 25, 50, 75, 100, 150, 200, 250, 300, 350, 400, 450,500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700,1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900,3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, or 4000 (orany integer between 25 and 4000), for example. The value of n in stillother examples can be in a range of 25-250, 50-250, 75-250, 100-250,150-250, 200-250, 25-200, 50-200, 75-200, 100-200, 150-200, 25-150,50-150, 75-150, 100-150, 25-100, 50-100, 75-100, 25-75, 50-75, or 25-50.

The molecular weight of a poly alpha-1,3-glucan ether compound hereincan be measured as number-average molecular weight (M_(n)) or asweight-average molecular weight (M_(w)). Alternatively, molecular weightcan be measured in Daltons or grams/mole. It may also be useful to referto the DP_(w) (weight average degree of polymerization) or DP_(n)(number average degree of polymerization) of the poly alpha-1,3-glucanpolymer component of the compound.

The M_(n) or M_(w) of a poly alpha-1,3-glucan ether compound herein maybe at least about 1000. Alternatively, the M_(n) or M_(w) can be atleast about 1000 to about 600000. Alternatively still, the M_(n) orM_(w) can be at least about 2000, 3000, 4000, 5000, 6000, 7000, 8000,9000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000,75000, 100000, 150000, 200000, 250000, 300000, 350000, 400000, 450000,500000, 550000, or 600000 (or any integer between 2000 and 600000), forexample.

Each R group in the formula of a poly alpha-1,3-glucan ether compoundherein can independently be an H or a positively charged organic group.As defined above, a positively charged organic group comprises a chainof one or more carbons having one or more hydrogens substituted withanother atom or functional group, where one or more of the substitutionsis with a positively charged group.

A positively charged group may be a substituted ammonium group, forexample. Examples of substituted ammonium groups are primary, secondary,tertiary and quaternary ammonium groups. Structure I depicts a primary,secondary, tertiary or quaternary ammonium group, depending on thecomposition of R₂, R₃ and R₄ in structure I. Each of R₂, R₃ and R₄ instructure I independently represent a hydrogen atom or an alkyl, aryl,cycloalkyl, aralkyl, or alkaryl group. Alternatively, each of R₂, R₃ andR₄ in can independently represent a hydrogen atom or an alkyl group. Analkyl group herein can be a methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, or decyl group, for example. Where two or three ofR₂, R₃ and R₄ are an alkyl group, they can be the same or differentalkyl groups.

A “primary ammonium poly alpha-1,3-glucan ether compound” herein cancomprise a positively charged organic group having an ammonium group. Inthis example, the positively charged organic group comprises structure Iin which each of R₂, R₃ and R₄ is a hydrogen atom. A non-limitingexample of such a positively charged organic group is represented bystructure II when each of R₂, R₃ and R₄ is a hydrogen atom. An exampleof a primary ammonium poly alpha-1,3-glucan ether compound can berepresented in shorthand as ammonium poly alpha-1,3-glucan ether. Itwould be understood that a first member (i.e., R₁) implied by “primary”in the above nomenclature is the chain of one or more carbons of thepositively charged organic group that is ether-linked to a glucosemonomer of poly alpha-1,3-glucan.

A “secondary ammonium poly alpha-1,3-glucan ether compound” herein cancomprise a positively charged organic group having a monoalkylammoniumgroup, for example. In this example, the positively charged organicgroup comprises structure I in which each of R₂ and R₃ is a hydrogenatom and R₄ is an alkyl group. A non-limiting example of such apositively charged organic group is represented by structure II wheneach of R₂ and R₃ is a hydrogen atom and R₄ is an alkyl group. Anexample of a secondary ammonium poly alpha-1,3-glucan ether compound canbe represented in shorthand herein as monoalkylammonium polyalpha-1,3-glucan ether (e.g., monomethyl-, monoethyl-, monopropyl-,monobutyl-, monopentyl-, monohexyl-, monoheptyl-, monooctyl-, monononyl-or monodecyl-ammonium poly alpha-1,3-glucan ether). It would beunderstood that a second member (i.e., R₁) implied by “secondary” in theabove nomenclature is the chain of one or more carbons of the positivelycharged organic group that is ether-linked to a glucose monomer of polyalpha-1,3-glucan.

A “tertiary ammonium poly alpha-1,3-glucan ether compound” herein cancomprise a positively charged organic group having a dialkylammoniumgroup, for example. In this example, the positively charged organicgroup comprises structure I in which R₂ is a hydrogen atom and each ofR₃ and R₄ is an alkyl group. A non-limiting example of such a positivelycharged organic group is represented by structure II when R₂ is ahydrogen atom and each of R₃ and R₄ is an alkyl group. An example of atertiary ammonium poly alpha-1,3-glucan ether compound can berepresented in shorthand as dialkylammonium poly alpha-1,3-glucan ether(e.g., dimethyl-, diethyl-, dipropyl-, dibutyl-, dipentyl-, dihexyl-,diheptyl-, dioctyl-, dinonyl- or didecyl-ammonium poly alpha-1,3-glucanether). It would be understood that a third member (i.e., R₁) implied by“tertiary” in the above nomenclature is the chain of one or more carbonsof the positively charged organic group that is ether-linked to aglucose monomer of poly alpha-1,3-glucan.

A “quaternary ammonium poly alpha-1,3-glucan ether compound” herein cancomprise a positively charged organic group having a trialkylammoniumgroup, for example. In this example, the positively charged organicgroup comprises structure I in which each of R₂, R₃ and R₄ is an alkylgroup. A non-limiting example of such a positively charged organic groupis represented by structure II when each of R₂, R₃ and R₄ is an alkylgroup. An example of a quaternary ammonium poly alpha-1,3-glucan ethercompound can be represented in shorthand as trialkylammonium polyalpha-1,3-glucan ether (e.g., trimethyl-, triethyl-, tripropyl-,tributyl-, tripentyl-, trihexyl-, triheptyl-, trioctyl-, trinonyl- ortridecyl-ammonium poly alpha-1,3-glucan ether). It would be understoodthat a fourth member (i.e., R₁) implied by “quaternary” in the abovenomenclature is the chain of one or more carbons of the positivelycharged organic group that is ether-linked to a glucose monomer of polyalpha-1,3-glucan.

Additional non-limiting examples of substituted ammonium groups that canserve as a positively charged group herein are represented in structureI when each of R₂, R₃ and R₄ independently represent a hydrogen atom; analkyl group such as a methyl, ethyl, or propyl group; an aryl group suchas a phenyl or naphthyl group; an aralkyl group such as a benzyl group;an alkaryl group; or a cycloalkyl group. Each of R₂, R₃ and R₄ mayfurther comprise an amino group or a hydroxyl group, for example.

The nitrogen atom in a substituted ammonium group represented bystructure I is bonded to a chain of one or more carbons as comprised ina positively charged organic group. This chain of one or more carbons(“carbon chain”) is ether-linked to a glucose monomer of polyalpha-1,3-glucan, and may have one or more substitutions in addition tothe substitution with the nitrogen atom of the substituted ammoniumgroup. There can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbons, forexample, in a carbon chain herein. To illustrate, the carbon chain ofstructure II is 3 carbon atoms in length.

Examples of a carbon chain of a positively charged organic group that donot have a substitution in addition to the substitution with apositively charged group include —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂CH₂CH₂CH₂— and —CH₂CH₂CH₂CH₂CH₂—. In each of these examples, thefirst carbon atom of the chain is ether-linked to a glucose monomer ofpoly alpha-1,3-glucan, and the last carbon atom of the chain is linkedto a positively charged group. Where the positively charged group is asubstituted ammonium group, the last carbon atom of the chain in each ofthese examples is represented by the C in structure I.

Where a carbon chain of a positively charged organic group has asubstitution in addition to a substitution with a positively chargedgroup, such additional substitution may be with one or more hydroxylgroups, oxygen atoms (thereby forming an aldehyde or ketone group),alkyl groups (e.g., methyl, ethyl, propyl, butyl), and/or additionalpositively charged groups. A positively charged group is typicallybonded to the terminal carbon atom of the carbon chain.

Examples of a carbon chain herein having one or more substitutions witha hydroxyl group include hydroxyalkyl (e.g., hydroxyethyl,hydroxypropyl, hydroxybutyl, hydroxypentyl) groups and dihydroxyalkyl(e.g., dihydroxyethyl, dihydroxypropyl, dihydroxybutyl, dihydroxypentyl)groups. Examples of hydroxyalkyl and dihydroxyalkyl (diol) carbon chainsinclude —CH(OH)—, —CH(OH)CH₂—, —C(OH)₂CH₂—, —CH₂CH(OH)CH₂—,—CH(OH)CH₂CH₂—, —CH(OH)CH(OH)CH₂—, —CH₂CH₂CH(OH)CH₂—, —CH₂CH(OH)CH₂CH₂—,—CH(OH)CH₂CH₂CH₂—, —CH₂CH(OH)CH(OH)CH₂—, —CH(OH)CH(OH)CH₂CH₂— and—CH(OH)CH₂CH(OH)CH₂—. In each of these examples, the first carbon atomof the chain is ether-linked to a glucose monomer of polyalpha-1,3-glucan, and the last carbon atom of the chain is linked to apositively charged group. Where the positively charged group is asubstituted ammonium group, the last carbon atom of the chain in each ofthese examples is represented by the C in structure I.

Examples of a carbon chain herein having one or more substitutions withan alkyl group include chains with one or more substituent methyl, ethyland/or propyl groups. Examples of methylalkyl groups include—CH(CH₃)CH₂CH₂— and —CH₂CH(CH₃)CH₂—, which are both propyl groups havinga methyl substitution. In each of these examples, the first carbon atomof the chain is ether-linked to a glucose monomer of polyalpha-1,3-glucan, and the last carbon atom of the chain is linked to apositively charged group. Where the positively charged group is asubstituted ammonium group, the last carbon atom of the chain in each ofthese examples is represented by the C in structure I.

Poly alpha-1,3-glucan ether compounds in certain embodiments disclosedherein may contain one type of positively charged organic group as an Rgroup. For example, one or more positively charged organic groupsether-linked to the glucose monomer of poly alpha-1,3-glucan may betrimethylammonium hydroxypropyl groups (structure II); the R groups inthis particular example would thus independently be hydrogen andtrimethylammonium hydroxypropyl groups.

Alternatively, poly alpha-1,3-glucan ether compounds disclosed hereincan contain two or more different types of positively charged organicgroups as R groups.

Poly alpha-1,3-glucan ether compounds herein can comprise at least onenonionic organic group and at least one anionic group, for example. Asanother example, poly alpha-1,3-glucan ether compounds herein cancomprise at least one nonionic organic group and at least one positivelycharged organic group.

The disclosed invention also concerns a hydrocolloid or aqueous solutioncomprising a poly alpha-1,3-glucan ether compound represented by thestructure:

Regarding the formula of this structure, n can be at least 6, and each Rcan independently be an H or a positively charged organic group.Furthermore, the poly alpha-1,3-glucan ether compound has a degree ofsubstitution of about 0.05 to about 3.0. The hydrocolloid or aqueoussolution comprising the poly alpha-1,3-glucan ether compound has aviscosity of at least about 10 centipoise (cPs). The polyalpha-1,3-glucan ether compound in a hydrocolloid or aqueous solutioncan be any of the ether compounds disclosed herein.

Hydrocolloids or aqueous solutions comprising a poly alpha-1,3-glucanether compound disclosed herein have a viscosity of at least about 10cPs. Alternatively, a hydrocolloid or aqueous solution herein has aviscosity of at least about 100, 250, 500, 750, 1000, 1500, 2000, 2500,3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500,9000, 9500, 10000, 10500, 11000, 12000, 13000, 14000, 15000, 20000,30000, 40000, 50000, 60000, 70000, 80000, 90000, or 100000 cPs (or anyinteger between 100 and 100000 cPs), for example.

Viscosity can be measured with the hydrocolloid or aqueous solution atany temperature between about 3° C. to about 110° C. (or any integerbetween 3 and 110° C.), for example. Alternatively, viscosity can bemeasured at a temperature between about 4° C. to 30° C., or about 20° C.to 25° C. Viscosity can be measured at atmospheric pressure (about 760torr) or any other higher or lower pressure.

The viscosity of a hydrocolloid or aqueous solution disclosed herein canbe measured using a viscometer or rheometer, or using any other meansknown in the art. It would be understood by those skilled in the artthat a rheometer can be used to measure the viscosity of thosehydrocolloids and aqueous solutions of the invention that exhibit shearthinning behavior or shear thickening behavior (i.e., liquids withviscosities that vary with flow conditions). The viscosity of suchembodiments can be measured at a rotational shear rate of about 10 to1000 rpm (revolutions per minute) (or any integer between 10 and 1000rpm), for example. Alternatively, viscosity can be measured at arotational shear rate of about 10, 60, 150, 250, or 600 rpm.

The pH of a hydrocolloid or aqueous solution disclosed herein can bebetween about 2.0 to about 12.0. Alternatively, pH can be about 2.0,3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0; or between 5.0 toabout 12.0; or between about 4.0 to about 8.0; or between about 3.0 and11.0. In certain embodiments, the viscosity of the hydrocolloid oraqueous solution does not largely fluctuate at a pH between about 3.0and 11.0.

An aqueous composition herein such as a hydrocolloid or aqueous solutioncan comprise a solvent having at least about 20 wt % water. In otherembodiments, a solvent is at least about 30, 40, 50, 60, 70, 80, 90, or100 wt % water (or any integer value between 20 and 100 wt %), forexample.

A poly alpha-1,3-glucan ether compound disclosed herein can be presentin a hydrocolloid or aqueous solution at a weight percentage (wt %) ofat least about 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%,0.8%, 0.9%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%,4.5%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%,19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, forexample.

A hydrocolloid or aqueous solution herein can comprise other componentsin addition to one or more poly alpha-1,3-glucan ether compound. Forexample, the hydrocolloid or aqueous solution can comprise one or moresalts such as a sodium salts (e.g., NaCl, Na₂SO₄). Other non-limitingexamples of salts include those having (i) an aluminum, ammonium,barium, calcium, chromium (II or III), copper (I or II), iron (II orIII), hydrogen, lead (II), lithium, magnesium, manganese (II or III),mercury (I or II), potassium, silver, sodium strontium, tin (II or IV),or zinc cation, and (ii) an acetate, borate, bromate, bromide,carbonate, chlorate, chloride, chlorite, chromate, cyanamide, cyanide,dichromate, dihydrogen phosphate, ferricyanide, ferrocyanide, fluoride,hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, hydrogensulfide, hydrogen sulfite, hydride, hydroxide, hypochlorite, iodate,iodide, nitrate, nitride, nitrite, oxalate, oxide, perchlorate,permanganate, peroxide, phosphate, phosphide, phosphite, silicate,stannate, stannite, sulfate, sulfide, sulfite, tartrate, or thiocyanateanion. Thus, any salt having a cation from (i) above and an anion from(ii) above can be in a hydrocolloid or aqueous solution, for example. Asalt can be present in a hydrocolloid or aqueous solution at a wt % ofabout 0.01% to about 10.00% (or any hundredth increment between 0.01 and10.00), for example.

A poly alpha-1,3-glucan ether compound herein is in a cationic form inthe hydrocolloid or aqueous solution. The cationic groups of a polyalpha-1,3-glucan ether compound herein can interact with salt anionsthat may be present in a hydrocolloid or aqueous solution. Such saltanions can be any of those listed above in (ii) (e.g., chloride anion).

In alternative embodiments, a composition comprising polyalpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compound hereincan be non-aqueous (e.g., a dry composition). Examples of suchembodiments include powders, granules, microcapsules, flakes, or anyother form or particulate matter. Other examples include largercompositions such as pellets, bars, kernels, beads, tablets, sticks, orother agglomerates. A non-aqueous or dry composition herein typicallyhas less than 3, 2, 1, 0.5 or 0.1 wt % water comprised therein.

A poly alpha-1,3-glucan ether compound comprised in certain embodimentsof the disclosed composition may be crosslinked using any means known inthe art. Such crosslinks may be borate crosslinks, where the borate isfrom any boron-containing compound (e.g., boric acid, diborates,tetraborates, pentaborates, polymeric compounds such as Polybor®,polymeric compounds of boric acid, alkali borates), for example.Alternatively, crosslinks can be provided with polyvalent metals such astitanium or zirconium. Titanium crosslinks may be provided, for example,using titanium IV-containing compounds such as titanium ammoniumlactate, titanium triethanolamine, titanium acetylacetonate, andpolyhydroxy complexes of titanium. Zirconium crosslinks can be providedusing zirconium IV-containing compounds such as zirconium lactate,zirconium carbonate, zirconium acetylacetonate, zirconiumtriethanolamine, zirconium diisopropylamine lactate and polyhydroxycomplexes of zirconium, for example. Alternatively still, crosslinks canbe provided with any crosslinking agent described in U.S. Pat. Nos.4,462,917, 4,464,270, 4,477,360 and 4,799,550, which are allincorporated herein by reference. A crosslinking agent (e.g., borate)may be present in an aqueous composition herein at a concentration ofabout 0.2% to 20 wt %, or about 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5,6, 7, 8, 9, 10, 15, or 20 wt %, for example.

A poly alpha-1,3-glucan ether compound disclosed herein that iscrosslinked typically has a higher viscosity in an aqueous solutioncompared to its non-crosslinked counterpart. In addition, a crosslinkedpoly alpha-1,3-glucan ether compound can have increased shear thickeningbehavior compared to its non-crosslinked counterpart.

A composition herein may optionally contain one or more active enzymes.Non-limiting examples of suitable enzymes include proteases, cellulases,hemicellulases, peroxidases, lipolytic enzymes (e.g., metallolipolyticenzymes), xylanases, lipases, phospholipases, esterases (e.g.,arylesterase, polyesterase), perhydrolases, cutinases, pectinases,pectate lyases, mannanases, keratinases, reductases, oxidases (e.g.,choline oxidase), phenoloxidases, lipoxygenases, ligninases,pullulanases, tannases, pentosanases, malanases, beta-glucanases,arabinosidases, hyaluronidases, chondroitinases, laccases,metalloproteinases, amadoriases, glucoamylases, arabinofuranosidases,phytases, isomerases, transferases and amylases. If an enzyme(s) isincluded, it may be comprised in a composition herein at about0.0001-0.1 wt % (e.g., 0.01-0.03 wt %) active enzyme (e.g., calculatedas pure enzyme protein), for example.

One or more cellulase enzymes may optionally be comprised in acomposition disclosed herein. A cellulase herein can have endocellulaseactivity (EC 3.2.1.4), exocellulase activity (EC 3.2.1.91), orcellobiase activity (EC 3.2.1.21). A cellulase herein is an “activecellulase” having activity under suitable conditions for maintainingcellulase activity; it is within the skill of the art to determine suchsuitable conditions. Besides being able to degrade cellulose, acellulase in certain embodiments can also degrade cellulose etherderivatives such as carboxymethyl cellulose. Examples of cellulose etherderivatives which are expected to not be stable to cellulase aredisclosed in U.S. Pat. Nos. 7,012,053, 7,056,880, 6,579,840, 7,534,759and 7,576,048.

A cellulase herein may be derived from any microbial source, such as abacteria or fungus. Chemically-modified cellulases or protein-engineeredmutant cellulases are included. Suitable cellulases include, but are notlimited to, cellulases from the genera Bacillus, Pseudomonas,Streptomyces, Trichoderma, Humicola, Fusarium, Thielavia and Acremonium.As other examples, a cellulase may be derived from Humicola insolens,Myceliophthora thermophila or Fusarium oxysporum; these and othercellulases are disclosed in U.S. Pat. Nos. 4,435,307, 5,648,263,5,691,178, 5,776,757 and 7,604,974, which are all incorporated herein byreference. Exemplary Trichoderma reesei cellulases are disclosed in U.S.Pat. Nos. 4,689,297, 5,814,501, 5,324,649, and International PatentAppl. Publ. Nos. WO92/06221 and WO92/06165, all of which areincorporated herein by reference. Exemplary Bacillus cellulases aredisclosed in U.S. Pat. No. 6,562,612, which is incorporated herein byreference. A cellulase, such as any of the foregoing, preferably is in amature form lacking an N-terminal signal peptide. Commercially availablecellulases useful herein include CELLUZYME® and CAREZYME® (NovozymesA/S); CLAZINASE® and PURADAX® HA (DuPont Industrial Biosciences), andKAC-500(B)® (Kao Corporation).

Alternatively, a cellulase herein may be produced by any means known inthe art, such as described in U.S. Pat. Nos. 4,435,307, 5,776,757 and7,604,974, which are incorporated herein by reference. For example, acellulase may be produced recombinantly in a heterologous expressionsystem, such as a microbial or fungal heterologous expression system.Examples of heterologous expression systems include bacterial (e.g., E.coli, Bacillus sp.) and eukaryotic systems. Eukaryotic systems canemploy yeast (e.g., Pichia sp., Saccharomyces sp.) or fungal (e.g.,Trichoderma sp. such as T. reesei, Aspergillus species such as A. niger)expression systems, for example.

One or more cellulases can be directly added as an ingredient whenpreparing the disclosed composition. Alternatively, one or morecellulases can be indirectly (inadvertently) provided in the disclosedcomposition. For example, cellulase can be provided in a compositionherein by virtue of being present in a non-cellulase enzyme preparationused for preparing the composition. Cellulase in compositions in whichcellulase is indirectly provided thereto can be present at about 0.1-10ppb (e.g., less than 1 ppm), for example. A benefit of a compositionherein, by virtue of employing a poly alpha-1,3-glucan ether compoundinstead of a cellulose ether compound, is that non-cellulase enzymepreparations that might have background cellulase activity can be usedwithout concern that the desired effects of the glucan ether will benegated by the background cellulase activity.

A cellulase in certain embodiments can be thermostable. Cellulasethermostability refers to the ability of the enzyme to retain activityafter exposure to an elevated temperature (e.g. about 60-70° C.) for aperiod of time (e.g., about 30-60 minutes). The thermostability of acellulase can be measured by its half-life (t½) given in minutes, hours,or days, during which time period half the cellulase activity is lostunder defined conditions.

A cellulase in certain embodiments can be stable to a wide range of pHvalues (e.g. neutral or alkaline pH such as pH of ˜7.0 to ˜11.0). Suchenzymes can remain stable for a predetermined period of time (e.g., atleast about 15 min., 30 min., or 1 hour) under such pH conditions.

At least one, two, or more cellulases may be included in thecomposition, for example. The total amount of cellulase in a compositionherein typically is an amount that is suitable for the purpose of usingcellulase in the composition (an “effective amount”). For example, aneffective amount of cellulase in a composition intended for improvingthe feel and/or appearance of a cellulose-containing fabric is an amountthat produces measurable improvements in the feel of the fabric (e.g.,improving fabric smoothness and/or appearance, removing pills andfibrils which tend to reduce fabric appearance sharpness). As anotherexample, an effective amount of cellulase in a fabric stonewashingcomposition herein is that amount which will provide the desired effect(e.g., to produce a worn and faded look in seams and on fabric panels).The amount of cellulase in a composition herein can also depend on theprocess parameters in which the composition is employed (e.g.,equipment, temperature, time, and the like) and cellulase activity, forexample. The effective concentration of cellulase in an aqueouscomposition in which a fabric is treated can be readily determined by askilled artisan. In fabric care processes, cellulase can be present inan aqueous composition (e.g., wash liquor) in which a fabric is treatedin a concentration that is minimally about 0.01-0.1 ppm total cellulaseprotein, or about 0.1-10 ppb total cellulase protein (e.g., less than 1ppm), to maximally about 100, 200, 500, 1000, 2000, 3000, 4000, or 5000ppm total cellulase protein, for example.

Poly alpha-1,3 glucan and/or poly alpha-1,3-glucan ethers herein aremostly or completely stable (resistant) to being degraded by cellulase.For example, the percent degradation of a poly alpha-1,3 glucan and/orpoly alpha-1,3-glucan ether compound by one or more cellulases is lessthan 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or is 0%. Such percentdegradation can be determined, for example, by comparing the molecularweight of polymer before and after treatment with a cellulase for aperiod of time (e.g., ˜24 hours).

Hydrocolloids and aqueous solutions of the invention can have shearthinning behavior or shear thickening behavior. Shear thinning behavioris observed as a decrease in viscosity of the hydrocolloid or aqueoussolution as shear rate increases, whereas shear thickening behavior isobserved as an increase in viscosity of the hydrocolloid or aqueoussolution as shear rate increases. Modification of the shear thinningbehavior or shear thickening behavior of an aqueous solution herein isdue to the admixture of a poly alpha-1,3-glucan ether composition to theaqueous composition. Thus, one or more poly alpha-1,3-glucan ethercompounds of the invention can be added to an aqueous liquid compositionto modify its rheological profile (i.e., the flow properties of theaqueous liquid, solution, or mixture are modified). Also, one or morepoly alpha-1,3-glucan ether compounds of the invention can be added toan aqueous composition to modify its viscosity.

The rheological properties of hydrocolloids and aqueous solutions of theinvention can be observed by measuring viscosity over an increasingrotational shear rate (e.g., from about 10 rpm to about 250 rpm). Forexample, shear thinning behavior of a hydrocolloid or aqueous solutiondisclosed herein can be observed as a decrease in viscosity (cPs) by atleast about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%,65%, 70%, 75%, 80%, 85%, 90%, or 95% (or any integer between 5% and 95%)as the rotational shear rate increases from about 10 rpm to 60 rpm, 10rpm to 150 rpm, 10 rpm to 250 rpm, 60 rpm to 150 rpm, 60 rpm to 250 rpm,or 150 rpm to 250 rpm. As another example, shear thickening behavior ofa hydrocolloid or aqueous solution disclosed herein can be observed asan increase in viscosity (cPs) by at least about 5%, 10%, 15%, 20%, 25%,30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%,100%, 125%, 150%, 175%, or 200% (or any integer between 5% and 200%) asthe rotational shear rate increases from about 10 rpm to 60 rpm, 10 rpmto 150 rpm, 10 rpm to 250 rpm, 60 rpm to 150 rpm, 60 rpm to 250 rpm, or150 rpm to 250 rpm.

A hydrocolloid or aqueous solution disclosed herein can be in the formof, and/or comprised in, a personal care product, pharmaceuticalproduct, food product, household product, or industrial product. Polyalpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds herein canbe used as thickening agents and/or dispersion agents in each of theseproducts. Such a thickening agent may be used in conjunction with one ormore other types of thickening agents if desired, such as thosedisclosed in U.S. Pat. No. 8,541,041, the disclosure of which isincorporated herein by reference.

Personal care products herein are not particularly limited and include,for example, skin care compositions, cosmetic compositions, antifungalcompositions, and antibacterial compositions. Personal care productsherein may be in the form of, for example, lotions, creams, pastes,balms, ointments, pomades, gels, liquids, combinations of these and thelike. The personal care products disclosed herein can include at leastone active ingredient, if desired. An active ingredient is generallyrecognized as an ingredient that causes an intended pharmacologicaleffect.

In certain embodiments, a skin care product can be applied to skin foraddressing skin damage related to a lack of moisture. A skin careproduct may also be used to address the visual appearance of skin (e.g.,reduce the appearance of flaky, cracked, and/or red skin) and/or thetactile feel of the skin (e.g., reduce roughness and/or dryness of theskin while improved the softness and subtleness of the skin). A skincare product typically may include at least one active ingredient forthe treatment or prevention of skin ailments, providing a cosmeticeffect, or for providing a moisturizing benefit to skin, such as zincoxide, petrolatum, white petrolatum, mineral oil, cod liver oil,lanolin, dimethicone, hard fat, vitamin A, allantoin, calamine, kaolin,glycerin, or colloidal oatmeal, and combinations of these. A skin careproduct may include one or more natural moisturizing factors such asceramides, hyaluronic acid, glycerin, squalane, amino acids,cholesterol, fatty acids, triglycerides, phospholipids,glycosphingolipids, urea, linoleic acid, glycosaminoglycans,mucopolysaccharide, sodium lactate, or sodium pyrrolidone carboxylate,for example. Other ingredients that may be included in a skin careproduct include, without limitation, glycerides, apricot kernel oil,canola oil, squalane, squalene, coconut oil, corn oil, jojoba oil,jojoba wax, lecithin, olive oil, safflower oil, sesame oil, shea butter,soybean oil, sweet almond oil, sunflower oil, tea tree oil, shea butter,palm oil, cholesterol, cholesterol esters, wax esters, fatty acids, andorange oil.

A personal care product herein can also be in the form of makeup,lipstick, mascara, rouge, foundation, blush, eyeliner, lip liner, lipgloss, other cosmetics, sunscreen, sun block, nail polish, mousse, hairspray, styling gel, nail conditioner, bath gel, shower gel, body wash,face wash, shampoo, hair conditioner (leave-in or rinse-out), creamrinse, hair dye, hair coloring product, hair shine product, hair serum,hair anti-frizz product, hair split-end repair product, lip balm, skinconditioner, cold cream, moisturizer, body spray, soap, body scrub,exfoliant, astringent, scruffing lotion, depilatory, permanent wavingsolution, antidandruff formulation, antiperspirant composition,deodorant, shaving product, pre-shaving product, after-shaving product,cleanser, skin gel, rinse, dentifrice composition, toothpaste, ormouthwash, for example.

A pharmaceutical product herein can be in the form of an emulsion,liquid, elixir, gel, suspension, solution, cream, or ointment, forexample. Also, a pharmaceutical product herein can be in the form of anyof the personal care products disclosed herein, such as an antibacterialor antifungal composition. A pharmaceutical product can further compriseone or more pharmaceutically acceptable carriers, diluents, and/orpharmaceutically acceptable salts. A poly alpha-1,3-glucan ethercompound disclosed herein can also be used in capsules, encapsulants,tablet coatings, and as an excipients for medicaments and drugs.

Non-limiting examples of food products herein include vegetable, meat,and soy patties; reformed seafood; reformed cheese sticks; cream soups;gravies and sauces; salad dressing; mayonnaise; onion rings; jams,jellies, and syrups; pie filling; potato products such as French friesand extruded fries; batters for fried foods, pancakes/waffles and cakes;pet foods; beverages; frozen desserts; ice cream; cultured dairyproducts such as cottage cheese, yogurt, cheeses, and sour creams; cakeicing and glazes; whipped topping; leavened and unleavened baked goods;and the like.

Poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds,hydrocolloids and aqueous compositions disclosed herein can be used toprovide one or more of the following physical properties to a foodproduct (or any personal care product, pharmaceutical product, orindustrial product): thickening, freeze/thaw stability, lubricity,moisture retention and release, texture, consistency, shape retention,emulsification, binding, suspension, dispersion, and gelation, forexample. Poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ethercompounds disclosed herein can typically be used in a food product at alevel of about 0.01 to about 5 wt %, for example.

A poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounddisclosed herein can be comprised in a foodstuff or any other ingestiblematerial (e.g., enteral pharmaceutical preparation) in an amount thatprovides the desired degree of thickening and/or dispersion. Forexample, the concentration or amount of a poly alpha-1,3-glucan and/orpoly alpha-1,3-glucan ether compound in a product, on a weight basis,can be about 0.1-3 wt %, 0.1-4 wt %, 0.1-5 wt %, or 0.1-10 wt %.

A household and/or industrial product herein can be in the form ofdrywall tape-joint compounds; mortars; grouts; cement plasters; sprayplasters; cement stucco; adhesives; pastes; wall/ceiling texturizers;binders and processing aids for tape casting, extrusion forming,injection molding and ceramics; spray adherents andsuspending/dispersing aids for pesticides, herbicides, and fertilizers;fabric care products such as fabric softeners and laundry detergents;hard surface cleaners; air fresheners; polymer emulsions; gels such aswater-based gels; surfactant solutions; paints such as water-basedpaints; protective coatings; adhesives; sealants and caulks; inks suchas water-based ink; metal-working fluids; emulsion-based metal cleaningfluids used in electroplating, phosphatizing, galvanizing and/or generalmetal cleaning operations; hydraulic fluids (e.g., those used forfracking in downhole operations); and aqueous mineral slurries, forexample.

Poly alpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compounddisclosed herein can be comprised in a personal care product,pharmaceutical product, household product, or industrial product in anamount that provides a desired degree of thickening or dispersion, forexample. Examples of a concentration or amount of a polyalpha-1,3-glucan ether compound in a product, on a weight basis, can beabout 0.1-3 wt %, 1-2 wt %, 1.5-2.5 wt %, 2.0 wt %, 0.1-4 wt %, 0.1-5 wt%, or 0.1-10 wt %.

Compositions disclosed herein can be in the form of a fabric carecomposition. A fabric care composition herein can be used for hand wash,machine wash and/or other purposes such as soaking and/or pretreatmentof fabrics, for example. A fabric care composition may take the form of,for example, a laundry detergent; fabric conditioner; any wash-, rinse-,or dryer-added product; unit dose; or spray. Fabric care compositions ina liquid form may be in the form of an aqueous composition as disclosedherein. In other aspects, a fabric care composition can be in a dry formsuch as a granular detergent or dryer-added fabric softener sheet. Othernon-limiting examples of fabric care compositions herein include:granular or powder-form all-purpose or heavy-duty washing agents;liquid, gel or paste-form all-purpose or heavy-duty washing agents;liquid or dry fine-fabric (e.g. delicates) detergents; cleaningauxiliaries such as bleach additives, “stain-stick”, or pre-treatments;substrate-laden products such as dry and wetted wipes, pads, or sponges;sprays and mists.

A detergent composition herein may be in any useful form, e.g., aspowders, granules, pastes, bars, unit dose, or liquid. A liquiddetergent may be aqueous, typically containing up to about 70 wt % ofwater and 0 wt % to about 30 wt % of organic solvent. It may also be inthe form of a compact gel type containing only about 30 wt % water.

A detergent composition herein typically comprises one or moresurfactants, wherein the surfactant is selected from nonionicsurfactants, anionic surfactants, cationic surfactants, ampholyticsurfactants, zwitterionic surfactants, semi-polar nonionic surfactantsand mixtures thereof. In some embodiments, the surfactant is present ata level of from about 0.1% to about 60%, while in alternativeembodiments the level is from about 1% to about 50%, while in stillfurther embodiments the level is from about 5% to about 40%, by weightof the detergent composition. A detergent will usually contain 0 wt % toabout 50 wt % of an anionic surfactant such as linearalkylbenzenesulfonate (LAS), alpha-olefinsulfonate (AOS), alkyl sulfate(fatty alcohol sulfate) (AS), alcohol ethoxysulfate (AEOS or AES),secondary alkanesulfonates (SAS), alpha-sulfo fatty acid methyl esters,alkyl- or alkenylsuccinic acid, or soap. In addition, a detergentcomposition may optionally contain 0 wt % to about 40 wt % of a nonionicsurfactant such as alcohol ethoxylate (AEO or AE), carboxylated alcoholethoxylates, nonylphenol ethoxylate, alkylpolyglycoside,alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fattyacid monoethanolamide, or polyhydroxy alkyl fatty acid amide (asdescribed for example in WO92/06154, which is incorporated herein byreference).

A detergent composition herein typically comprises one or more detergentbuilders or builder systems. In some embodiments incorporating at leastone builder, the cleaning compositions comprise at least about 1%, fromabout 3% to about 60%, or even from about 5% to about 40%, builder byweight of the composition. Builders include, but are not limited to,alkali metal, ammonium and alkanolammonium salts of polyphosphates,alkali metal silicates, alkaline earth and alkali metal carbonates,aluminosilicates, polycarboxylate compounds, etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonicacid, and carboxymethyloxysuccinic acid, various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, citric acid,oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof. Indeed, it iscontemplated that any suitable builder will find use in variousembodiments of the present invention. Examples of a detergent builder orcomplexing agent include zeolite, diphosphate, triphosphate,phosphonate, citrate, nitrilotriacetic acid (NTA),ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaaceticacid (DTMPA), alkyl- or alkenylsuccinic acid, soluble silicates orlayered silicates (e.g., SKS-6 from Hoechst). A detergent may also beunbuilt, i.e., essentially free of detergent builder.

In some embodiments, builders form water-soluble hardness ion complexes(e.g., sequestering builders), such as citrates and polyphosphates(e.g., sodium tripolyphosphate and sodium tripolyphosphate hexahydrate,potassium tripolyphosphate, and mixed sodium and potassiumtripolyphosphate, etc.). It is contemplated that any suitable builderwill find use in the present invention, including those known in the art(See, e.g., EP2100949).

In some embodiments, builders for use herein include phosphate buildersand non-phosphate builders. In some embodiments, the builder is aphosphate builder. In some embodiments, the builder is a non-phosphatebuilder. If present, builders are used in a level of from 0.1% to 80%,or from 5% to 60%, or from 10% to 50%, by weight of the composition. Insome embodiments, the product comprises a mixture of phosphate andnon-phosphate builders. Suitable phosphate builders includemono-phosphates, di-phosphates, tri-polyphosphates oroligomeric-polyphosphates, including the alkali metal salts of thesecompounds, including the sodium salts. In some embodiments, a buildercan be sodium tripolyphosphate (STPP). Additionally, the composition cancomprise carbonate and/or citrate, preferably citrate that helps toachieve a neutral pH composition. Other suitable non-phosphate buildersinclude homopolymers and copolymers of polycarboxylic acids and theirpartially or completely neutralized salts, monomeric polycarboxylicacids and hydroxycarboxylic acids and their salts. In some embodiments,salts of the above mentioned compounds include ammonium and/or alkalimetal salts, i.e., lithium, sodium, and potassium salts, includingsodium salts. Suitable polycarboxylic acids include acyclic, alicyclic,hetero-cyclic and aromatic carboxylic acids, wherein in someembodiments, they can contain at least two carboxyl groups which are ineach case separated from one another by, in some instances, no more thantwo carbon atoms.

A detergent composition herein can comprise at least one chelatingagent. Suitable chelating agents include, but are not limited to copper,iron and/or manganese chelating agents and mixtures thereof. Inembodiments in which at least one chelating agent is used, thecomposition comprises from about 0.1% to about 15%, or even from about3.0% to about 10%, chelating agent by weight of the composition.

A detergent composition herein can comprise at least one deposition aid.Suitable deposition aids include, but are not limited to, polyethyleneglycol, polypropylene glycol, polycarboxylate, soil release polymerssuch as polytelephthalic acid, clays such as kaolinite, montmorillonite,atapulgite, illite, bentonite, halloysite, and mixtures thereof.

A detergent composition herein can comprise one or more dye transferinhibiting agents. Suitable polymeric dye transfer inhibiting agentsinclude, but are not limited to, polyvinylpyrrolidone polymers,polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles ormixtures thereof. Additional dye transfer inhibiting agents includemanganese phthalocyanine, peroxidases, polyvinylpyrrolidone polymers,polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylim idazole, polyvinyloxazolidones and polyvinylimidazoles and/ormixtures thereof; chelating agents examples of which includeethylene-diamine-tetraacetic acid (EDTA); diethylene triamine pentamethylene phosphonic acid (DTPMP); hydroxy-ethane diphosphonic acid(HEDP); ethylenediamine N,N′-disuccinic acid (EDDS); methyl glycinediacetic acid (MGDA); diethylene triamine penta acetic acid (DTPA);propylene diamine tetracetic acid (PDT A); 2-hydroxypyridine-N-oxide(HPNO); or methyl glycine diacetic acid (MGDA); glutamic acidN,N-diacetic acid (N,N-dicarboxymethyl glutamic acid tetrasodium salt(GLDA); nitrilotriacetic acid (NTA); 4,5-dihydroxy-m-benzenedisulfonicacid; citric acid and any salts thereof;N-hydroxyethylethylenediaminetri-acetic acid (HEDTA),triethylenetetraaminehexaacetic acid (TTNA), N-hydroxyethyliminodiaceticacid (HEIDA), dihydroxyethylglycine (DHEG),ethylenediaminetetrapropionic acid (EDTP) and derivatives thereof, whichcan be used alone or in combination with any of the above. Inembodiments in which at least one dye transfer inhibiting agent is used,a composition herein may comprise from about 0.0001% to about 10%, fromabout 0.01% to about 5%, or even from about 0.1% to about 3%, by weightof the composition.

A detergent composition herein can comprise silicates. In some of theseembodiments, sodium silicates (e.g., sodium disilicate, sodiummetasilicate, and/or crystalline phyllosilicates) find use. In someembodiments, silicates are present at a level of from about 1% to about20% by weight of the composition. In some embodiments, silicates arepresent at a level of from about 5% to about 15% by weight of thecomposition.

A detergent composition herein can comprise dispersants. Suitablewater-soluble organic materials include, but are not limited to thehomo- or co-polymeric acids or their salts, in which the polycarboxylicacid comprises at least two carboxyl radicals separated from each otherby not more than two carbon atoms.

A detergent composition herein may additionally comprise one or moreenzymes. Examples of enzymes include proteases, cellulases,hemicellulases, peroxidases, lipolytic enzymes (e.g., metallolipolyticenzymes), xylanases, lipases, phospholipases, esterases (e.g.,arylesterase, polyesterase), perhydrolases, cutinases, pectinases,pectate lyases, mannanases, keratinases, reductases, oxidases (e.g.,choline oxidase, phenoloxidase), phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,beta-glucanases, arabinosidases, hyaluronidases, chondroitinases,laccases, metalloproteinases, amadoriases, glucoamylases,alpha-amylases, beta-amylases, galactosidases, galactanases, catalases,carageenases, hyaluronidases, keratinases, lactases, ligninases,peroxidases, phosphatases, polygalacturonases, pullulanases,rhamnogalactouronases, tannases, transglutaminases, xyloglucanases,xylosidases, metalloproteases, arabinofuranosidases, phytases,isomerases, transferases and/or amylases in any combination.

Any cellulase disclosed above is contemplated for use in the discloseddetergent compositions. Suitable cellulases include, but are not limitedto Humicola insolens cellulases (See e.g., U.S. Pat. No. 4,435,307).Exemplary cellulases contemplated for use herein are those having colorcare benefit for a textile. Examples of cellulases that provide a colorcare benefit are disclosed in EP0495257, EP0531372, EP531315,WO96/11262, WO96/29397, WO94/07998; WO98/12307; WO95/24471, WO98/08940,and U.S. Pat. Nos. 5,457,046, 5,686,593 and 5,763,254, all of which areincorporated herein by reference. Examples of commercially availablecellulases useful in a detergent include CELLUSOFT®, CELLUCLEAN®,CELLUZYME®, and CAREZYME® (Novo Nordisk A/S and Novozymes A/S);CLAZINASE®, PURADAX HA®, and REVITALENZ™ (DuPont IndustrialBiosciences); BIOTOUCH® (AB Enzymes); and KAC-500(B)™ (Kao Corporation).Additional cellulases are disclosed in, e.g., U.S. Pat. No. 7,595,182,U.S. Pat. No. 8,569,033, U.S. Pat. No. 7,138,263, U.S. Pat. No.3,844,890, U.S. Pat. No. 4,435,307, U.S. Pat. No. 4,435,307, andGB2095275.

In some embodiments of the present invention, the detergent compositionsof the present invention can comprise one or more enzymes, each at alevel from about 0.00001% to about 10% by weight of the composition andthe balance of cleaning adjunct materials by weight of composition. Insome other embodiments of the present invention, the detergentcompositions also comprise each enzyme at a level of about 0.0001% toabout 10%, about 0.001% to about 5%, about 0.001% to about 2%, about0.005% to about 0.5%, enzyme by weight of the composition.

Suitable proteases include those of animal, vegetable or microbialorigin. In some embodiments, microbial proteases are used. In someembodiments, chemically or genetically modified mutants are included. Insome embodiments, the protease is a serine protease, preferably analkaline microbial protease or a trypsin-like protease. Examples ofalkaline proteases include subtilisins, especially those derived fromBacillus (e.g., subtilisin, lentus, amyloliquefaciens, subtilisinCarlsberg, subtilisin 309, subtilisin 147 and subtilisin 168).Additional examples include those mutant proteases described in U.S.Pat. No. RE34606, U.S. Pat. Nos. 5,955,340, 5,700,676, 6,312,936 and6,482,628, all of which are incorporated herein by reference. Additionalprotease examples include, but are not limited to, trypsin (e.g., ofporcine or bovine origin), and the Fusarium protease described inWO89/06270. In some embodiments, commercially available protease enzymesinclude, but are not limited to, MAXATASE®, MAXACAL™, MAXAPEM™,OPTICLEAN®, OPTIMASE®, PROPERASE®, PURAFECT®, PURAFECT® OXP, PURAMAX™,EXCELLASE™, PREFERENZ™ proteases (e.g. P100, P110, P280), EFFECTENZ™proteases (e.g. P1000, P1050, P2000), EXCELLENZ™ proteases (e.g. P1000),ULTIMASE®, and PURAFAST™ (Genencor); ALCALASE®, SAVINASE®, PRIMASE®,DURAZYM™, POLARZYME®, OVOZYME®, KANNASE®, LIQUANASE®, NEUTRASE®, RELASE®and ESPERASE® (Novozymes); BLAP™ and BLAP™ variants (HenkelKommanditgesellschaft auf Aktien, Duesseldorf, Germany), and KAP (B.alkalophilus subtilisin; Kao Corp., Tokyo, Japan). Various proteases aredescribed in WO95/23221, WO92/21760, WO09/149200, WO09/149144,WO09/149145, WO11/072099, WO10/056640, WO10/056653, WO11/140364,WO12/151534, U.S. Pat. Publ. No. 2008/0090747, and U.S. Pat. Nos.5,801,039, 5,340,735, 5,500,364, 5,855,625, RE34606, U.S. Pat. Nos.5,955,340, 5,700,676, 6,312,936, 6,482,628, 8,530,219, and various otherpatents. In some further embodiments, neutral metalloproteases find usein the present invention, including but not limited to, the neutralmetalloproteases described in WO1999014341, WO1999033960, WO1999014342,WO1999034003, WO2007044993, WO2009058303 and WO2009058661, all of whichare incorporated herein by reference. Exemplary metalloproteases includenprE, the recombinant form of neutral metalloprotease expressed inBacillus subtilis (See e.g., WO07/044993), and PMN, the purified neutralmetalloprotease from Bacillus amyloliquefaciens.

Suitable mannanases include, but are not limited to, those of bacterialor fungal origin. Chemically or genetically modified mutants areincluded in some embodiments. Various mannanases are known which finduse in the present invention (See, e.g., U.S. Pat. Nos. 6,566,114,6,602,842, and 6,440,991, all of which are incorporated herein byreference). Commercially available mannanases that find use in thepresent invention include, but are not limited to MANNASTAR®,PURABRITE™, and MANNAWAY®.

Suitable lipases include those of bacterial or fungal origin. Chemicallymodified, proteolytically modified, or protein engineered mutants areincluded. Examples of useful lipases include those from the generaHumicola (e.g., H. lanuginosa, EP258068 and EP305216; H. insolens,WO96/13580), Pseudomonas (e.g., P. alcaligenes or P. pseudoalcaligenes,EP218272; P. cepacia, EP331376; P. stutzeri, GB1372034; P. fluorescensand Pseudomonas sp. strain SD 705, WO95/06720 and WO96/27002; P.wisconsinensis, WO96/12012); and Bacillus (e.g., B. subtilis, Dartois etal., Biochemica et Biophysica Acta 1131:253-360; B. stearothermophilus,JP64/744992; B. pumilus, WO91/16422). Furthermore, a number of clonedlipases find use in some embodiments of the present invention, includingbut not limited to, Penicillium camembertii lipase (See, Yamaguchi etal., Gene 103:61-67 [1991]), Geotricum candidum lipase (See, Schimada etal., J. Biochem., 106:383-388 [1989]), and various Rhizopus lipases suchas R. delemar lipase (See, Hass et al., Gene 109:117-113 [1991]), a R.niveus lipase (Kugimiya et al., Biosci. Biotech. Biochem. 56:716-719[1992]) and R. oryzae lipase. Additional lipases useful herein include,for example, those disclosed in WO92/05249, WO94/01541, WO95/35381,WO96/00292, WO95/30744, WO94/25578, WO95/14783, WO95/22615, WO97/04079,WO97/07202, EP407225 and EP260105. Other types of lipase polypeptideenzymes such as cutinases also find use in some embodiments of thepresent invention, including but not limited to, cutinase derived fromPseudomonas mendocina (See, WO88/09367), and cutinase derived fromFusarium solani pisi (See, WO90/09446). Examples of certain commerciallyavailable lipase enzymes useful herein include M1 LIPASE™, LUMA FAST™,and LIPOMAX™ (Genencor); LIPEX®, LIPOLASE® and LIPOLASE® ULTRA(Novozymes); and LIPASE P™ “Amano” (Amano Pharmaceutical Co. Ltd.,Japan).

Suitable polyesterases include, for example, those disclosed inWO01/34899, WO01/14629 and U.S. Pat. No. 6,933,140.

A detergent composition herein can also comprise 2,6-beta-D-fructanhydrolase, which is effective for removal/cleaning of certain biofilmspresent on household and/or industrial textiles/laundry.

Suitable amylases include, but are not limited to those of bacterial orfungal origin. Chemically or genetically modified mutants are includedin some embodiments. Amylases that find use in the present invention,include, but are not limited to, alpha-amylases obtained from B.licheniformis (See e.g., GB1296839). Additional suitable amylasesinclude those disclosed in WO9510603, WO9526397, WO9623874, WO9623873,WO9741213, WO9919467, WO0060060, WO0029560, WO9923211, WO9946399,WO0060058, WO0060059, WO9942567, WO0114532, WO02092797, WO0166712,WO0188107, WO0196537, WO0210355, WO9402597, WO0231124, WO9943793,WO9943794, WO2004113551, WO2005001064, WO2005003311, WO0164852,WO2006063594, WO2006066594, WO2006066596, WO2006012899, WO2008092919,WO2008000825, WO2005018336, WO2005066338, WO2009140504, WO2005019443,WO2010091221, WO2010088447, WO0134784, WO2006012902, WO2006031554,WO2006136161, WO2008101894, WO2010059413, WO2011098531, WO2011080352,WO2011080353, WO2011080354, WO2011082425, WO2011082429, WO2011076123,WO2011087836, WO2011076897, WO94183314, WO9535382, WO9909183, WO9826078,WO9902702, WO9743424, WO9929876, WO9100353, WO9605295, WO9630481,WO9710342, WO2008088493, WO2009149419, WO2009061381, WO2009100102,WO2010104675, WO2010117511, and WO2010115021, all of which areincorporated herein by reference.

Suitable amylases include, for example, commercially available amylasessuch as STAINZYME®, STAINZYME PLUS®, NATALASE®, DURAMYL®, TERMAMYL®,TERMAMYL ULTRA®, FUNGAMYL® and BAN™ (Novo Nordisk A/S and NovozymesA/S); RAPIDASE®, POWERASE®, PURASTAR® and PREFERENZ™ (DuPont IndustrialBiosciences).

Suitable peroxidases/oxidases contemplated for use in the compositionsinclude those of plant, bacterial or fungal origin. Chemically modifiedor protein engineered mutants are included. Examples of peroxidasesuseful herein include those from the genus Coprinus (e.g., C. cinereus,WO93/24618, WO95/10602, and WO98/15257), as well as those referenced inWO2005056782, WO2007106293, WO2008063400, WO2008106214, andWO2008106215. Commercially available peroxidases useful herein include,for example, GUARDZYME™ (Novo Nordisk A/S and Novozymes A/S).

In some embodiments, peroxidases are used in combination with hydrogenperoxide or a source thereof (e.g., a percarbonate, perborate orpersulfate) in the compositions of the present invention. In somealternative embodiments, oxidases are used in combination with oxygen.Both types of enzymes are used for “solution bleaching” (i.e., toprevent transfer of a textile dye from a dyed fabric to another fabricwhen the fabrics are washed together in a wash liquor), preferablytogether with an enhancing agent (See e.g., WO94/12621 and WO95/01426).Suitable peroxidases/oxidases include, but are not limited to, those ofplant, bacterial or fungal origin. Chemically or genetically modifiedmutants are included in some embodiments.

Enzymes that may be comprised in a detergent composition herein may bestabilized using conventional stabilizing agents, e.g., a polyol such aspropylene glycol or glycerol; a sugar or sugar alcohol; lactic acid;boric acid or a boric acid derivative (e.g., an aromatic borate ester).

A detergent composition herein may contain about 1 wt % to about 65 wt %of a detergent builder or complexing agent such as zeolite, diphosphate,triphosphate, phosphonate, citrate, nitrilotriacetic acid (NTA),ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaaceticacid (DTMPA), alkyl- or alkenylsuccinic acid, soluble silicates orlayered silicates (e.g., SKS-6 from Hoechst). A detergent may also beunbuilt, i.e., essentially free of detergent builder.

A detergent composition in certain embodiments may comprise one or moreother types of polymers in addition to a poly alpha-1,3-glucan and/orpoly alpha-1,3-glucan ether compound. Examples of other types ofpolymers useful herein include carboxymethyl cellulose (CMC),poly(vinylpyrrolidone) (PVP), polyethylene glycol (PEG), poly(vinylalcohol) (PVA), polycarboxylates such as polyacrylates, maleic/acrylicacid copolymers and lauryl methacrylate/acrylic acid copolymers.

A detergent composition herein may contain a bleaching system. Forexample, a bleaching system can comprise an H₂O₂ source such asperborate or percarbonate, which may be combined with a peracid-formingbleach activator such as tetraacetylethylenediamine (TAED) ornonanoyloxybenzenesulfonate (NOBS). Alternatively, a bleaching systemmay comprise peroxyacids (e.g., amide, imide, or sulfone typeperoxyacids). Alternatively still, a bleaching system can be anenzymatic bleaching system comprising perhydrolase, for example, such asthe system described in WO2005/056783.

A detergent composition herein may also contain conventional detergentingredients such as fabric conditioners, clays, foam boosters, sudssuppressors, anti-corrosion agents, soil-suspending agents, anti-soilredeposition agents, dyes, bactericides, tarnish inhibitors, opticalbrighteners, or perfumes. The pH of a detergent composition herein(measured in aqueous solution at use concentration) is usually neutralor alkaline (e.g., pH of about 7.0 to about 11.0).

Particular forms of detergent compositions that can be adapted forpurposes disclosed herein are disclosed in, for example,US20090209445A1, US20100081598A1, U.S. Pat. No. 7,001,878B2,EP1504994B1, WO2001085888A2, WO2003089562A1, WO2009098659A1,WO2009098660A1, WO2009112992A1, WO2009124160A1, WO2009152031 A1,WO2010059483A1, WO2010088112A1, WO2010090915A1, WO2010135238A1,WO2011094687A1, WO2011094690A1, WO2011127102A1, WO2011163428A1,WO2008000567A1, WO2006045391 A1, WO2006007911 A1, WO2012027404A1,EP1740690B1, WO2012059336A1, U.S. Pat. No. 6,730,646B1, WO2008087426A1,WO2010116139A1, and WO2012104613A1, all of which are incorporated hereinby reference.

Laundry detergent compositions herein can optionally be heavy duty (allpurpose) laundry detergent compositions. Exemplary heavy duty laundrydetergent compositions comprise a detersive surfactant (10%-40% wt/wt),including an anionic detersive surfactant (selected from a group oflinear or branched or random chain, substituted or unsubstituted alkylsulphates, alkyl sulphonates, alkyl alkoxylated sulphate, alkylphosphates, alkyl phosphonates, alkyl carboxylates, and/or mixturesthereof), and optionally non-ionic surfactant (selected from a group oflinear or branched or random chain, substituted or unsubstituted alkylalkoxylated alcohol, e.g., C8-C18 alkyl ethoxylated alcohols and/orC6-C12 alkyl phenol alkoxylates), where the weight ratio of anionicdetersive surfactant (with a hydrophilic index (HIc) of from 6.0 to 9)to non-ionic detersive surfactant is greater than 1:1. Suitabledetersive surfactants also include cationic detersive surfactants(selected from a group of alkyl pyridinium compounds, alkyl quaternaryammonium compounds, alkyl quaternary phosphonium compounds, alkylternary sulphonium compounds, and/or mixtures thereof); zwitterionicand/or amphoteric detersive surfactants (selected from a group ofalkanolamine sulpho-betaines); ampholytic surfactants; semi-polarnon-ionic surfactants and mixtures thereof.

A detergent herein such as a heavy duty laundry detergent compositionmay optionally include, a surfactancy boosting polymer consisting ofamphiphilic alkoxylated grease cleaning polymers (selected from a groupof alkoxylated polymers having branched hydrophilic and hydrophobicproperties, such as alkoxylated polyalkylenimines in the range of 0.05wt %-10 wt %) and/or random graft polymers (typically comprising ofhydrophilic backbone comprising monomers selected from the groupconsisting of: unsaturated C1-C6 carboxylic acids, ethers, alcohols,aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydride,saturated polyalcohols such as glycerol, and mixtures thereof; andhydrophobic side chain(s) selected from the group consisting of: C4-C25alkyl group, polypropylene, polybutylene, vinyl ester of a saturatedC1-C6 mono-carboxylic acid, C1-C6 alkyl ester of acrylic or methacrylicacid, and mixtures thereof.

A detergent herein such as a heavy duty laundry detergent compositionmay optionally include additional polymers such as soil release polymers(include anionically end-capped polyesters, for example SRP1, polymerscomprising at least one monomer unit selected from saccharide,dicarboxylic acid, polyol and combinations thereof, in random or blockconfiguration, ethylene terephthalate-based polymers and co-polymersthereof in random or block configuration, for example REPEL-O-TEX SF,SF-2 AND SRP6, TEXCARE SRA100, SRA300, SRN100, SRN170, SRN240, SRN300AND SRN325, MARLOQUEST SL), anti-redeposition polymers (0.1 wt % to 10wt %), include carboxylate polymers, such as polymers comprising atleast one monomer selected from acrylic acid, maleic acid (or maleicanhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid,citraconic acid, methylenemalonic acid, and any mixture thereof,vinylpyrrolidone homopolymer, and/or polyethylene glycol, molecularweight in the range of from 500 to 100,000 Da); and polymericcarboxylate (such as maleate/acrylate random copolymer or polyacrylatehomopolymer).

A detergent herein such as a heavy duty laundry detergent compositionmay optionally further include saturated or unsaturated fatty acids,preferably saturated or unsaturated C12-C24 fatty acids (0 wt % to 10 wt%); deposition aids in addition to a poly alpha-1,3-glucan ethercompound disclosed herein (examples for which include polysaccharides,cellulosic polymers, poly diallyl dimethyl ammonium halides (DADMAC),and co-polymers of DAD MAC with vinyl pyrrolidone, acrylamides,imidazoles, imidazolinium halides, and mixtures thereof, in random orblock configuration, cationic guar gum, cationic starch, cationicpolyacrylamides, and mixtures thereof.

A detergent herein such as a heavy duty laundry detergent compositionmay optionally further include dye transfer inhibiting agents, examplesof which include manganese phthalocyanine, peroxidases,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylim idazole, polyvinyloxazolidones andpolyvinylimidazoles and/or mixtures thereof; chelating agents, examplesof which include ethylene-diamine-tetraacetic acid (EDTA), diethylenetriamine penta methylene phosphonic acid (DTPMP), hydroxy-ethanediphosphonic acid (HEDP), ethylenediamine N,N′-disuccinic acid (EDDS),methyl glycine diacetic acid (MGDA), diethylene triamine penta aceticacid (DTPA), propylene diamine tetracetic acid (PDTA),2-hydroxypyridine-N-oxide (HPNO), or methyl glycine diacetic acid(MGDA), glutamic acid N,N-diacetic acid (N,N-dicarboxymethyl glutamicacid tetrasodium salt (GLDA), nitrilotriacetic acid (NTA),4,5-dihydroxy-m-benzenedisulfonic acid, citric acid and any saltsthereof, N-hydroxyethylethylenediaminetriacetic acid (HEDTA),triethylenetetraaminehexaacetic acid (TTNA), N-hydroxyethyliminodiaceticacid (HEIDA), dihydroxyethylglycine (DHEG),ethylenediaminetetrapropionic acid (EDTP), and derivatives thereof.

A detergent herein such as a heavy duty laundry detergent compositionmay optionally include silicone or fatty-acid based suds suppressors;hueing dyes, calcium and magnesium cations, visual signalingingredients, anti-foam (0.001 wt % to about 4.0 wt %), and/or astructurant/thickener (0.01 wt % to 5 wt %) selected from the groupconsisting of diglycerides and triglycerides, ethylene glycoldistearate, microcrystalline cellulose, microfiber cellulose,biopolymers, xanthan gum, gellan gum, and mixtures thereof). Suchstructurant/thickener would be in addition to the one or more polyalpha-1,3-glucan compounds comprised in the detergent.

A detergent herein can be in the form of a heavy duty dry/solid laundrydetergent composition, for example. Such a detergent may include: (i) adetersive surfactant, such as any anionic detersive surfactant disclosedherein, any non-ionic detersive surfactant disclosed herein, anycationic detersive surfactant disclosed herein, any zwitterionic and/oramphoteric detersive surfactant disclosed herein, any ampholyticsurfactant, any semi-polar non-ionic surfactant, and mixtures thereof;(ii) a builder, such as any phosphate-free builder (e.g., zeolitebuilders in the range of 0 wt % to less than 10 wt %), any phosphatebuilder (e.g., sodium tri-polyphosphate in the range of 0 wt % to lessthan 10 wt %), citric acid, citrate salts and nitrilotriacetic acid, anysilicate salt (e.g., sodium or potassium silicate or sodiummeta-silicate in the range of 0 wt % to less than 10 wt %); anycarbonate salt (e.g., sodium carbonate and/or sodium bicarbonate in therange of 0 wt % to less than 80 wt %), and mixtures thereof; (iii) ableaching agent, such as any photobleach (e.g., sulfonated zincphthalocyanines, sulfonated aluminum phthalocyanines, xanthenes dyes,and mixtures thereof), any hydrophobic or hydrophilic bleach activator(e.g., dodecanoyl oxybenzene sulfonate, decanoyl oxybenzene sulfonate,decanoyl oxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulfonate, tetraacetyl ethylene diamine-TAED,nonanoyloxybenzene sulfonate-NOBS, nitrile quats, and mixtures thereof),any source of hydrogen peroxide (e.g., inorganic perhydrate salts,examples of which include mono or tetra hydrate sodium salt ofperborate, percarbonate, persulfate, perphosphate, or persilicate), anypreformed hydrophilic and/or hydrophobic peracids (e.g., percarboxylicacids and salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, and mixtures thereof); and/or (iv)any other components such as a bleach catalyst (e.g., imine bleachboosters examples of which include iminium cations and polyions, iminiumzwitterions, modified amines, modified amine oxides, N-sulphonyl imines,N-phosphonyl imines, N-acyl imines, thiadiazole dioxides,perfluoroimines, cyclic sugar ketones, and mixtures thereof), and ametal-containing bleach catalyst (e.g., copper, iron, titanium,ruthenium, tungsten, molybdenum, or manganese cations along with anauxiliary metal cations such as zinc or aluminum and a sequestrate suchas EDTA, ethylenediaminetetra(methylenephosphonic acid).

Compositions disclosed herein can be in the form of a dishwashingdetergent composition. Examples of dishwashing detergents includeautomatic dishwashing detergents (typically used in dishwasher machines)and hand-washing dish detergents. A dishwashing detergent compositioncan be in any dry or liquid/aqueous form as disclosed herein, forexample. Components that may be included in certain embodiments of adishwashing detergent composition include, for example, one or more of aphosphate; oxygen- or chlorine-based bleaching agent; non-ionicsurfactant; alkaline salt (e.g., metasilicates, alkali metal hydroxides,sodium carbonate); any active enzyme disclosed herein; anti-corrosionagent (e.g., sodium silicate); anti-foaming agent; additives to slowdown the removal of glaze and patterns from ceramics; perfume;anti-caking agent (in granular detergent); starch (in tablet-baseddetergents); gelling agent (in liquid/gel based detergents); and/or sand(powdered detergents).

Dishwashing detergents such as an automatic dishwasher detergent orliquid dishwashing detergent can comprise (i) a non-ionic surfactant,including any ethoxylated non-ionic surfactant, alcohol alkoxylatedsurfactant, epoxy-capped poly(oxyalkylated) alcohol, or amine oxidesurfactant present in an amount from 0 to 10 wt %; (ii) a builder, inthe range of about 5-60 wt %, including any phosphate builder (e.g.,mono-phosphates, di-phosphates, tri-polyphosphates, otheroligomeric-polyphosphates, sodium tripolyphosphate-STPP), anyphosphate-free builder (e.g., amino acid-based compounds includingmethyl-glycine-diacetic acid [MGDA] and salts or derivatives thereof,glutamic-N,N-diacetic acid [GLDA] and salts or derivatives thereof,iminodisuccinic acid (IDS) and salts or derivatives thereof, carboxymethyl inulin and salts or derivatives thereof, nitrilotriacetic acid[NTA], diethylene triamine penta acetic acid [DTPA], B-alaninediaceticacid [B-ADA] and salts thereof), homopolymers and copolymers ofpoly-carboxylic acids and partially or completely neutralized saltsthereof, monomeric polycarboxylic acids and hydroxycarboxylic acids andsalts thereof in the range of 0.5 wt % to 50 wt %, orsulfonated/carboxylated polymers in the range of about 0.1 wt % to about50 wt %; (iii) a drying aid in the range of about 0.1 wt % to about 10wt % (e.g., polyesters, especially anionic polyesters, optionallytogether with further monomers with 3 to 6 functionalities—typicallyacid, alcohol or ester functionalities which are conducive topolycondensation, polycarbonate-, polyurethane- and/orpolyurea-polyorganosiloxane compounds or precursor compounds thereof,particularly of the reactive cyclic carbonate and urea type); (iv) asilicate in the range from about 1 wt % to about 20 wt % (e.g., sodiumor potassium silicates such as sodium disilicate, sodium meta-silicateand crystalline phyllosilicates); (v) an inorganic bleach (e.g.,perhydrate salts such as perborate, percarbonate, perphosphate,persulfate and persilicate salts) and/or an organic bleach (e.g.,organic peroxyacids such as diacyl- and tetraacylperoxides, especiallydiperoxydodecanedioic acid, diperoxytetradecanedioic acid, anddiperoxyhexadecanedioic acid); (vi) a bleach activator (e.g., organicperacid precursors in the range from about 0.1 wt % to about 10 wt %)and/or bleach catalyst (e.g., manganese triazacyclononane and relatedcomplexes; Co, Cu, Mn, and Fe bispyridylamine and related complexes; andpentamine acetate cobalt(III) and related complexes); (vii) a metal careagent in the range from about 0.1 wt % to 5 wt % (e.g., benzatriazoles,metal salts and complexes, and/or silicates); and/or (viii) any activeenzyme disclosed herein in the range from about 0.01 to 5.0 mg of activeenzyme per gram of automatic dishwashing detergent composition, and anenzyme stabilizer component (e.g., oligosaccharides, polysaccharides,and inorganic divalent metal salts).

Various examples of detergent formulations comprising at least one polyalpha-1,3-glucan ether compound (e.g., a quaternary ammonium polyalpha-1,3-glucan such as trimethylammonium hydroxypropyl polyalpha-1,3-glucan) are disclosed below (1-19):

1) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: linear alkylbenzenesulfonate(calculated as acid) at about 7-12 wt %; alcohol ethoxysulfate (e.g.,C12-18 alcohol, 1-2 ethylene oxide [EO]) or alkyl sulfate (e.g., C16-18)at about 1-4 wt %; alcohol ethoxylate (e.g., C14-15 alcohol) at about5-9 wt %; sodium carbonate at about 14-20 wt %; soluble silicate (e.g.,Na₂O 2SiO₂) at about 2-6 wt %; zeolite (e.g., NaAlSiO₄) at about 15-22wt %; sodium sulfate at about 0-6 wt %; sodium citrate/citric acid atabout 0-15 wt %; sodium perborate at about 11-18 wt %; TAED at about 2-6wt %; poly alpha-1,3-glucan ether up to about 2 wt %; other polymers(e.g., maleic/acrylic acid copolymer, PVP, PEG) at about 0-3 wt %;optionally an enzyme(s) (calculated as pure enzyme protein) at about0.0001-0.1 wt %; and minor ingredients (e.g., suds suppressors,perfumes, optical brightener, photobleach) at about 0-5 wt %.

2) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: linear alkylbenzenesulfonate(calculated as acid) at about 6-11 wt %; alcohol ethoxysulfate (e.g.,C12-18 alcohol, 1-2 EO) or alkyl sulfate (e.g., C16-18) at about 1-3 wt%; alcohol ethoxylate (e.g., C14-15 alcohol) at about 5-9 wt %; sodiumcarbonate at about 15-21 wt %; soluble silicate (e.g., Na₂O 2SiO₂) atabout 1-4 wt %; zeolite (e.g., NaAlSiO₄) at about 24-34 wt %; sodiumsulfate at about 4-10 wt %; sodium citrate/citric acid at about 0-15 wt%; sodium perborate at about 11-18 wt %; TAED at about 2-6 wt %; polyalpha-1,3-glucan ether up to about 2 wt %; other polymers (e.g.,maleic/acrylic acid copolymer, PVP, PEG) at about 1-6 wt %; optionallyan enzyme(s) (calculated as pure enzyme protein) at about 0.0001-0.1 wt%; and minor ingredients (e.g., suds suppressors, perfumes, opticalbrightener, photobleach) at about 0-5 wt %.

3) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: linear alkylbenzenesulfonate(calculated as acid) at about 5-9 wt %; alcohol ethoxysulfate (e.g.,C12-18 alcohol, 7 EO) at about 7-14 wt %; soap as fatty acid (e.g.,C16-22 fatty acid) at about 1-3 wt %; sodium carbonate at about 10-17 wt%; soluble silicate (e.g., Na₂O 2SiO₂) at about 3-9 wt %; zeolite (e.g.,NaAlSiO₄) at about 23-33 wt %; sodium sulfate at about 0-4 wt %; sodiumperborate at about 8-16 wt %; TAED at about 2-8 wt %; phosphonate (e.g.,EDTMPA) at about 0-1 wt %; poly alpha-1,3-glucan ether up to about 2 wt%; other polymers (e.g., maleic/acrylic acid copolymer, PVP, PEG) atabout 0-3 wt %; optionally an enzyme(s) (calculated as pure enzymeprotein) at about 0.0001-0.1 wt %; and minor ingredients (e.g., sudssuppressors, perfumes, optical brightener) at about 0-5 wt %.

4) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: linear alkylbenzenesulfonate(calculated as acid) at about 8-12 wt %; alcohol ethoxylate (e.g.,C12-18 alcohol, 7 EO) at about 10-25 wt %; sodium carbonate at about14-22 wt %; soluble silicate (e.g., Na₂O 2SiO₂) at about 1-5 wt %;zeolite (e.g., NaAlSiO₄) at about 25-35 wt %; sodium sulfate at about0-10 wt %; sodium perborate at about 8-16 wt %; TAED at about 2-8 wt %;phosphonate (e.g., EDTMPA) at about 0-1 wt %; poly alpha-1,3-glucanether up to about 2 wt %; other polymers (e.g., maleic/acrylic acidcopolymer, PVP, PEG) at about 1-3 wt %; optionally an enzyme(s)(calculated as pure enzyme protein) at about 0.0001-0.1 wt %; and minoringredients (e.g., suds suppressors, perfumes) at about 0-5 wt %.

5) An aqueous liquid detergent composition comprising: linearalkylbenzenesulfonate (calculated as acid) at about 15-21 wt %; alcoholethoxylate (e.g., C12-18 alcohol, 7 EO; or C12-15 alcohol, 5 EO) atabout 12-18 wt %; soap as fatty acid (e.g., oleic acid) at about 3-13 wt%; alkenylsuccinic acid (C12-14) at about 0-13 wt %; aminoethanol atabout 8-18 wt %; citric acid at about 2-8 wt %; phosphonate at about 0-3wt %; poly alpha-1,3-glucan ether up to about 2 wt %; other polymers(e.g., PVP, PEG) at about 0-3 wt %; borate at about 0-2 wt %; ethanol atabout 0-3 wt %; propylene glycol at about 8-14 wt %; optionally anenzyme(s) (calculated as pure enzyme protein) at about 0.0001-0.1 wt %;and minor ingredients (e.g., dispersants, suds suppressors, perfume,optical brightener) at about 0-5 wt %.

6) An aqueous structured liquid detergent composition comprising: linearalkylbenzenesulfonate (calculated as acid) at about 15-21 wt %; alcoholethoxylate (e.g., C12-18 alcohol, 7 EO; or C12-15 alcohol, 5 EO) atabout 3-9 wt %; soap as fatty acid (e.g., oleic acid) at about 3-10 wt%; zeolite (e.g., NaAlSiO₄) at about 14-22 wt %; potassium citrate about9-18 wt %; borate at about 0-2 wt %; poly alpha-1,3-glucan ether up toabout 2 wt %; other polymers (e.g., PVP, PEG) at about 0-3 wt %; ethanolat about 0-3 wt %; anchoring polymers (e.g., lauryl methacrylate/acrylicacid copolymer, molar ratio 25:1, MW 3800) at about 0-3 wt %; glycerolat about 0-5 wt %; optionally an enzyme(s) (calculated as pure enzymeprotein) at about 0.0001-0.1 wt %; and minor ingredients (e.g.,dispersants, suds suppressors, perfume, optical brightener) at about 0-5wt %.

7) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: fatty alcohol sulfate at about5-10 wt %, ethoxylated fatty acid monoethanolamide at about 3-9 wt %;soap as fatty acid at about 0-3 wt %; sodium carbonate at about 5-10 wt%; soluble silicate (e.g., Na₂O 2SiO₂) at about 1-4 wt %; zeolite (e.g.,NaAlSiO₄) at about 20-40 wt %; sodium sulfate at about 2-8 wt %; sodiumperborate at about 12-18 wt %; TAED at about 2-7 wt %; polyalpha-1,3-glucan ether up to about 2 wt %; other polymers (e.g.,maleic/acrylic acid copolymer, PEG) at about 1-5 wt %; optionally anenzyme(s) (calculated as pure enzyme protein) at about 0.0001-0.1 wt %;and minor ingredients (e.g., optical brightener, suds suppressors,perfumes) at about 0-5 wt %.

8) A detergent composition formulated as a granulate comprising: linearalkylbenzenesulfonate (calculated as acid) at about 8-14 wt %;ethoxylated fatty acid monoethanolamide at about 5-11 wt %; soap asfatty acid at about 0-3 wt %; sodium carbonate at about 4-10 wt %;soluble silicate (e.g., Na₂O 2SiO₂) at about 1-4 wt %; zeolite (e.g.,NaAlSiO₄) at about 30-50 wt %; sodium sulfate at about 3-11 wt %; sodiumcitrate at about 5-12 wt %; poly alpha-1,3-glucan ether up to about 2 wt%; other polymers (e.g., PVP, maleic/acrylic acid copolymer, PEG) atabout 1-5 wt %; optionally an enzyme(s) (calculated as pure enzymeprotein) at about 0.0001-0.1 wt %; and minor ingredients (e.g., sudssuppressors, perfumes) at about 0-5 wt %.

9) A detergent composition formulated as a granulate comprising: linearalkylbenzenesulfonate (calculated as acid) at about 6-12 wt %; nonionicsurfactant at about 1-4 wt %; soap as fatty acid at about 2-6 wt %;sodium carbonate at about 14-22 wt %; zeolite (e.g., NaAlSiO₄) at about18-32 wt %; sodium sulfate at about 5-20 wt %; sodium citrate at about3-8 wt %; sodium perborate at about 4-9 wt %; bleach activator (e.g.,NOBS or TAED) at about 1-5 wt %; poly alpha-1,3-glucan ether up to about2 wt %; other polymers (e.g., polycarboxylate or PEG) at about 1-5 wt %;optionally an enzyme(s) (calculated as pure enzyme protein) at about0.0001-0.1 wt %; and minor ingredients (e.g., optical brightener,perfume) at about 0-5 wt %.

10) An aqueous liquid detergent composition comprising: linearalkylbenzenesulfonate (calculated as acid) at about 15-23 wt %; alcoholethoxysulfate (e.g., C12-15 alcohol, 2-3 EO) at about 8-15 wt %; alcoholethoxylate (e.g., C12-15 alcohol, 7 EO; or C12-15 alcohol, 5 EO) atabout 3-9 wt %; soap as fatty acid (e.g., lauric acid) at about 0-3 wt%; aminoethanol at about 1-5 wt %; sodium citrate at about 5-10 wt %;hydrotrope (e.g., sodium toluenesulfonate) at about 2-6 wt %; borate atabout 0-2 wt %; poly alpha-1,3-glucan ether up to about 1 wt %; ethanolat about 1-3 wt %; propylene glycol at about 2-5 wt %; optionally anenzyme(s) (calculated as pure enzyme protein) at about 0.0001-0.1 wt %;and minor ingredients (e.g., dispersants, perfume, optical brighteners)at about 0-5 wt %.

11) An aqueous liquid detergent composition comprising: linearalkylbenzenesulfonate (calculated as acid) at about 20-32 wt %; alcoholethoxylate (e.g., C12-15 alcohol, 7 EO; or C12-15 alcohol, 5 EO) atabout 6-12 wt %; aminoethanol at about 2-6 wt %; citric acid at about8-14 wt %; borate at about 1-3 wt %; poly alpha-1,3-glucan ether up toabout 2 wt %; ethanol at about 1-3 wt %; propylene glycol at about 2-5wt %; other polymers (e.g., maleic/acrylic acid copolymer, anchoringpolymer such as lauryl methacrylate/acrylic acid copolymer) at about 0-3wt %; glycerol at about 3-8 wt %; optionally an enzyme(s) (calculated aspure enzyme protein) at about 0.0001-0.1 wt %; and minor ingredients(e.g., hydrotropes, dispersants, perfume, optical brighteners) at about0-5 wt %.

12) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: anionic surfactant (e.g., linearalkylbenzenesulfonate, alkyl sulfate, alpha-olefinsulfonate, alpha-sulfofatty acid methyl esters, alkanesulfonates, soap) at about 25-40 wt %;nonionic surfactant (e.g., alcohol ethoxylate) at about 1-10 wt %;sodium carbonate at about 8-25 wt %; soluble silicate (e.g., Na₂O 2SiO₂)at about 5-15 wt %; sodium sulfate at about 0-5 wt %; zeolite (NaAlSiO₄)at about 15-28 wt %; sodium perborate at about 0-20 wt %; bleachactivator (e.g., TAED or NOBS) at about 0-5 wt %; poly alpha-1,3-glucanether up to about 2 wt %; optionally an enzyme(s) (calculated as pureenzyme protein) at about 0.0001-0.1 wt %; and minor ingredients (e.g.,perfume, optical brighteners) at about 0-3 wt %.

13) Detergent compositions as described in (1)-(12) above, but in whichall or part of the linear alkylbenzenesulfonate is replaced by C12-C18alkyl sulfate.

14) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: C12-C18 alkyl sulfate at about9-15 wt %; alcohol ethoxylate at about 3-6 wt %; polyhydroxy alkyl fattyacid amide at about 1-5 wt %; zeolite (e.g., NaAlSiO₄) at about 10-20 wt%; layered disilicate (e.g., SK56 from Hoechst) at about 10-20 wt %;sodium carbonate at about 3-12 wt %; soluble silicate (e.g., Na₂O 2SiO₂)at 0-6 wt %; sodium citrate at about 4-8 wt %; sodium percarbonate atabout 13-22 wt %; TAED at about 3-8 wt %; poly alpha-1,3-glucan ether upto about 2 wt %; other polymers (e.g., polycarboxylates and PVP) atabout 0-5 wt %; optionally an enzyme(s) (calculated as pure enzymeprotein) at about 0.0001-0.1 wt %; and minor ingredients (e.g., opticalbrightener, photobleach, perfume, suds suppressors) at about 0-5 wt %.

15) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: C12-C18 alkyl sulfate at about4-8 wt %; alcohol ethoxylate at about 11-15 wt %; soap at about 1-4 wt%; zeolite MAP or zeolite A at about 35-45 wt %; sodium carbonate atabout 2-8 wt %; soluble silicate (e.g., Na₂O 2SiO₂) at 0-4 wt %; sodiumpercarbonate at about 13-22 wt %; TAED at about 1-8 wt %; polyalpha-1,3-glucan ether up to about 3 wt %; other polymers (e.g.,polycarboxylates and PVP) at about 0-3 wt %; optionally an enzyme(s)(calculated as pure enzyme protein) at about 0.0001-0.1 wt %; and minoringredients (e.g., optical brightener, phosphonate, perfume) at about0-3 wt %.

16) Detergent formulations as described in (1)-(15) above, but thatcontain a stabilized or encapsulated peracid, either as an additionalcomponent or as a substitute for an already specified bleach system(s).

17) Detergent compositions as described in (1), (3), (7), (9) and (12)above, but in which perborate is replaced by percarbonate.

18) Detergent compositions as described in (1), (3), (7), (9), (12),(14) and (15) above, but that additionally contain a manganese catalyst.A manganese catalyst, for example, is one of the compounds described byHage et al. (1994, Nature 369:637-639), which is incorporated herein byreference.

19) Detergent compositions formulated as a non-aqueous detergent liquidcomprising a liquid non-ionic surfactant (e.g., a linear alkoxylatedprimary alcohol), a builder system (e.g., phosphate), polyalpha-1,3-glucan ether, optionally an enzyme(s), and alkali. Thedetergent may also comprise an anionic surfactant and/or bleach system.

It is believed that numerous commercially available detergentformulations can be adapted to include a poly alpha-1,3-glucan ethercompound. Examples include PUREX® ULTRAPACKS (Henkel), FINISH® QUANTUM(Reckitt Benckiser), CLOROX™ 2 PACKS (Clorox), OXICLEAN MAX FORCE POWERPAKS (Church & Dwight), TIDE® STAIN RELEASE, CASCADE® ACTIONPACS, andTIDE® PODS™ (Procter & Gamble).

Compositions disclosed herein can be in the form of an oral carecomposition. Examples of oral care compositions include dentifrices,toothpaste, mouth wash, mouth rinse, chewing gum, and edible strips thatprovide some form of oral care (e.g., treatment or prevention ofcavities [dental caries], gingivitis, plaque, tartar, and/or periodontaldisease). An oral care composition can also be for treating an “oralsurface”, which encompasses any soft or hard surface within the oralcavity including surfaces of the tongue, hard and soft palate, buccalmucosa, gums and dental surfaces. A “dental surface” herein is a surfaceof a natural tooth or a hard surface of artificial dentition including acrown, cap, filling, bridge, denture, or dental implant, for example.

One or more poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ethercompounds comprised in an oral care composition typically are providedtherein as a thickening agent and/or dispersion agent, which may beuseful to impart a desired consistency and/or mouth feel to thecomposition. An oral care composition herein can comprise about0.01-15.0 wt % (e.g., ˜0.1-10 wt % or ˜0.1-5.0 wt %, ˜0.1-2.0 wt %) ofone or more poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ethercompounds disclosed herein (e.g., a quaternary ammonium polyalpha-1,3-glucan such as trimethylammonium hydroxypropyl polyalpha-1,3-glucan), for example. One or more other thickening agentsand/or dispersion agents can also be provided in an oral carecomposition herein, such as a carboxyvinyl polymer, carrageenan (e.g.,L-carrageenan), natural gum (e.g., karaya, xanthan, gum arabic,tragacanth), colloidal magnesium aluminum silicate, or colloidal silica,for example.

An oral care composition herein may be a toothpaste or other dentifrice,for example. Such compositions, as well as any other oral carecomposition herein, can additionally comprise, without limitation, oneor more of an anticaries agent, antimicrobial or antibacterial agent,anticalculus or tartar control agent, surfactant, abrasive, pH-modifyingagent, foam modulator, humectant, flavorant, sweetener,pigment/colorant, whitening agent, and/or other suitable components.Examples of oral care compositions to which one or more polyalpha-1,3-glucan ether compounds can be added are disclosed in U.S.Patent Appl. Publ. Nos. 2006/0134025, 2002/0022006 and 2008/0057007,which are incorporated herein by reference.

An anticaries agent herein can be an orally acceptable source offluoride ions. Suitable sources of fluoride ions include fluoride,monofluorophosphate and fluorosilicate salts as well as amine fluorides,including olaflur(N′-octadecyltrimethylendiamine-N,N,N′-tris(2-ethanol)-dihydrofluoride),for example. An anticaries agent can be present in an amount providing atotal of about 100-20000 ppm, about 200-5000 ppm, or about 500-2500 ppm,fluoride ions to the composition, for example. In oral care compositionsin which sodium fluoride is the sole source of fluoride ions, an amountof about 0.01-5.0 wt %, about 0.05-1.0 wt %, or about 0.1-0.5 wt %,sodium fluoride can be present in the composition, for example.

An antimicrobial or antibacterial agent suitable for use in an oral carecomposition herein includes, for example, phenolic compounds (e.g.,4-allylcatechol; p-hydroxybenzoic acid esters such as benzylparaben,butylparaben, ethylparaben, methylparaben and propylparaben;2-benzylphenol; butylated hydroxyanisole; butylated hydroxytoluene;capsaicin; carvacrol; creosol; eugenol; guaiacol; halogenatedbisphenolics such as hexachlorophene and bromochlorophene;4-hexylresorcinol; 8-hydroxyquinoline and salts thereof; salicylic acidesters such as menthyl salicylate, methyl salicylate and phenylsalicylate; phenol; pyrocatechol; salicylanilide; thymol; halogenateddiphenylether compounds such as triclosan and triclosan monophosphate),copper (II) compounds (e.g., copper (II) chloride, fluoride, sulfate andhydroxide), zinc ion sources (e.g., zinc acetate, citrate, gluconate,glycinate, oxide, and sulfate), phthalic acid and salts thereof (e.g.,magnesium monopotassium phthalate), hexetidine, octenidine,sanguinarine, benzalkonium chloride, domiphen bromide, alkylpyridiniumchlorides (e.g. cetylpyridinium chloride, tetradecylpyridinium chloride,N-tetradecyl-4-ethylpyridinium chloride), iodine, sulfonamides,bisbiguanides (e.g., alexidine, chlorhexidine, chlorhexidinedigluconate), piperidino derivatives (e.g., delmopinol, octapinol),magnolia extract, grapeseed extract, rosemary extract, menthol,geraniol, citral, eucalyptol, antibiotics (e.g., augmentin, amoxicillin,tetracycline, doxycycline, minocycline, metronidazole, neomycin,kanamycin, clindamycin), and/or any antibacterial agents disclosed inU.S. Pat. No. 5,776,435, which is incorporated herein by reference. Oneor more antimicrobial agents can optionally be present at about 0.01-10wt % (e.g., 0.1-3 wt %), for example, in the disclosed oral carecomposition.

An anticalculus or tartar control agent suitable for use in an oral carecomposition herein includes, for example, phosphates and polyphosphates(e.g., pyrophosphates), polyaminopropanesulfonic acid (AMPS), zinccitrate trihydrate, polypeptides (e.g., polyaspartic and polyglutamicacids), polyolefin sulfonates, polyolefin phosphates, diphosphonates(e.g., azacycloalkane-2,2-diphosphonates such asazacycloheptane-2,2-diphosphonic acid), N-methylazacyclopentane-2,3-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonicacid (EHDP), ethane-1-amino-1,1-diphosphonate, and/or phosphonoalkanecarboxylic acids and salts thereof (e.g., their alkali metal andammonium salts). Useful inorganic phosphate and polyphosphate saltsinclude, for example, monobasic, dibasic and tribasic sodium phosphates,sodium tripolyphosphate, tetrapolyphosphate, mono-, di-, tri- andtetra-sodium pyrophosphates, disodium dihydrogen pyrophosphate, sodiumtrimetaphosphate, sodium hexametaphosphate, or any of these in whichsodium is replaced by potassium or ammonium. Other useful anticalculusagents in certain embodiments include anionic polycarboxylate polymers(e.g., polymers or copolymers of acrylic acid, methacrylic, and maleicanhydride such as polyvinyl methyl ether/maleic anhydride copolymers).Still other useful anticalculus agents include sequestering agents suchas hydroxycarboxylic acids (e.g., citric, fumaric, malic, glutaric andoxalic acids and salts thereof) and aminopolycarboxylic acids (e.g.,EDTA). One or more anticalculus or tartar control agents can optionallybe present at about 0.01-50 wt % (e.g., about 0.05-25 wt % or about0.1-15 wt %), for example, in the disclosed oral care composition.

A surfactant suitable for use in an oral care composition herein may beanionic, non-ionic, or amphoteric, for example. Suitable anionicsurfactants include, without limitation, water-soluble salts of C₈₋₂₀alkyl sulfates, sulfonated monoglycerides of C₈₋₂₀ fatty acids,sarcosinates, and taurates. Examples of anionic surfactants includesodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodiumlauryl sarcosinate, sodium lauryl isoethionate, sodium laurethcarboxylate and sodium dodecyl benzenesulfonate. Suitable non-ionicsurfactants include, without limitation, poloxamers, polyoxyethylenesorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates,tertiary amine oxides, tertiary phosphine oxides, and dialkylsulfoxides. Suitable amphoteric surfactants include, without limitation,derivatives of C₈₋₂₀ aliphatic secondary and tertiary amines having ananionic group such as a carboxylate, sulfate, sulfonate, phosphate orphosphonate. An example of a suitable amphoteric surfactant iscocoamidopropyl betaine. One or more surfactants are optionally presentin a total amount of about 0.01-10 wt % (e.g., about 0.05-5.0 wt % orabout 0.1-2.0 wt %), for example, in the disclosed oral carecomposition.

An abrasive suitable for use in an oral care composition herein mayinclude, for example, silica (e.g., silica gel, hydrated silica,precipitated silica), alumina, insoluble phosphates, calcium carbonate,and resinous abrasives (e.g., a urea-formaldehyde condensation product).Examples of insoluble phosphates useful as abrasives herein areorthophosphates, polymetaphosphates and pyrophosphates, and includedicalcium orthophosphate dihydrate, calcium pyrophosphate, beta-calciumpyrophosphate, tricalcium phosphate, calcium polymetaphosphate andinsoluble sodium polymetaphosphate. One or more abrasives are optionallypresent in a total amount of about 5-70 wt % (e.g., about 10-56 wt % orabout 15-30 wt %), for example, in the disclosed oral care composition.The average particle size of an abrasive in certain embodiments is about0.1-30 microns (e.g., about 1-20 microns or about 5-15 microns).

An oral care composition in certain embodiments may comprise at leastone pH-modifying agent. Such agents may be selected to acidify, makemore basic, or buffer the pH of a composition to a pH range of about2-10 (e.g., pH ranging from about 2-8, 3-9, 4-8, 5-7, 6-10, or 7-9).Examples of pH-modifying agents useful herein include, withoutlimitation, carboxylic, phosphoric and sulfonic acids; acid salts (e.g.,monosodium citrate, disodium citrate, monosodium malate); alkali metalhydroxides (e.g. sodium hydroxide, carbonates such as sodium carbonate,bicarbonates, sesquicarbonates); borates; silicates; phosphates (e.g.,monosodium phosphate, trisodium phosphate, pyrophosphate salts); andimidazole.

A foam modulator suitable for use in an oral care composition herein maybe a polyethylene glycol (PEG), for example. High molecular weight PEGsare suitable, including those having an average molecular weight ofabout 200000-7000000 (e.g., about 500000-5000000 or about1000000-2500000), for example. One or more PEGs are optionally presentin a total amount of about 0.1-10 wt % (e.g. about 0.2-5.0 wt % or about0.25-2.0 wt %), for example, in the disclosed oral care composition.

An oral care composition in certain embodiments may comprise at leastone humectant. A humectant in certain embodiments may be a polyhydricalcohol such as glycerin, sorbitol, xylitol, or a low molecular weightPEG. Most suitable humectants also may function as a sweetener herein.One or more humectants are optionally present in a total amount of about1.0-70 wt % (e.g., about 1.0-50 wt %, about 2-25 wt %, or about 5-15 wt%), for example, in the disclosed oral care composition.

A natural or artificial sweetener may optionally be comprised in an oralcare composition herein. Examples of suitable sweeteners includedextrose, sucrose, maltose, dextrin, invert sugar, mannose, xylose,ribose, fructose, levulose, galactose, corn syrup (e.g., high fructosecorn syrup or corn syrup solids), partially hydrolyzed starch,hydrogenated starch hydrolysate, sorbitol, mannitol, xylitol, maltitol,isomalt, aspartame, neotame, saccharin and salts thereof,dipeptide-based intense sweeteners, and cyclamates. One or moresweeteners are optionally present in a total amount of about 0.005-5.0wt %, for example, in the disclosed oral care composition.

A natural or artificial flavorant may optionally be comprised in an oralcare composition herein. Examples of suitable flavorants includevanillin; sage; marjoram; parsley oil; spearmint oil; cinnamon oil; oilof wintergreen (methylsalicylate); peppermint oil; clove oil; bay oil;anise oil; eucalyptus oil; citrus oils; fruit oils; essences such asthose derived from lemon, orange, lime, grapefruit, apricot, banana,grape, apple, strawberry, cherry, or pineapple; bean- and nut-derivedflavors such as coffee, cocoa, cola, peanut, or almond; and adsorbed andencapsulated flavorants. Also encompassed within flavorants herein areingredients that provide fragrance and/or other sensory effect in themouth, including cooling or warming effects. Such ingredients include,without limitation, menthol, menthyl acetate, menthyl lactate, camphor,eucalyptus oil, eucalyptol, anethole, eugenol, cassia, oxanone,Irisone®, propenyl guaiethol, thymol, linalool, benzaldehyde,cinnamaldehyde, N-ethyl-p-menthan-3-carboxamine,N,2,3-trimethyl-2-isopropylbutanamide, 3-(1-menthoxy)-propane-1,2-diol,cinnamaldehyde glycerol acetal (CGA), and menthone glycerol acetal(MGA). One or more flavorants are optionally present in a total amountof about 0.01-5.0 wt % (e.g., about 0.1-2.5 wt %), for example, in thedisclosed oral care composition.

An oral care composition in certain embodiments may comprise at leastone bicarbonate salt. Any orally acceptable bicarbonate can be used,including alkali metal bicarbonates such as sodium or potassiumbicarbonate, and ammonium bicarbonate, for example. One or morebicarbonate salts are optionally present in a total amount of about0.1-50 wt % (e.g., about 1-20 wt %), for example, in the disclosed oralcare composition.

An oral care composition in certain embodiments may comprise at leastone whitening agent and/or colorant. A suitable whitening agent is aperoxide compound such as any of those disclosed in U.S. Pat. No.8,540,971, which is incorporated herein by reference. Suitable colorantsherein include pigments, dyes, lakes and agents imparting a particularluster or reflectivity such as pearling agents, for example. Specificexamples of colorants useful herein include talc; mica; magnesiumcarbonate; calcium carbonate; magnesium silicate; magnesium aluminumsilicate; silica; titanium dioxide; zinc oxide; red, yellow, brown andblack iron oxides; ferric ammonium ferrocyanide; manganese violet;ultramarine; titaniated mica; and bismuth oxychloride. One or morecolorants are optionally present in a total amount of about 0.001-20 wt% (e.g., about 0.01-10 wt % or about 0.1-5.0 wt %), for example, in thedisclosed oral care composition.

Additional components that can optionally be included in an oralcomposition herein include one or more enzymes (above), vitamins, andanti-adhesion agents, for example. Examples of vitamins useful hereininclude vitamin C, vitamin E, vitamin B5, and folic acid. Examples ofsuitable anti-adhesion agents include solbrol, ficin, and quorum-sensinginhibitors.

The disclosed invention also concerns a method for increasing theviscosity of an aqueous composition. This method comprises contactingone or more poly alpha-1,3-glucan ether compounds disclosed herein withthe aqueous composition. This step results in increasing the viscosityof the aqueous composition. The poly alpha-1,3-glucan ether compound(s)used in this method can be represented by the structure:

Regarding the formula of this structure, n can be at least 6, and each Rcan independently be an H or a positively charged organic group.Furthermore, the poly alpha-1,3-glucan ether compound has a degree ofsubstitution of about 0.05 to about 3.0. Any hydrocolloid and aqueoussolution disclosed herein can be produced using this method.

An aqueous composition herein can be water (e.g., de-ionized water), anaqueous solution, or a hydrocolloid, for example. The viscosity of anaqueous composition before the contacting step, measured at about 20-25°C., can be about 0-10000 cPs (or any integer between 0-10000 cPs), forexample. Since the aqueous composition can be a hydrocolloid or the likein certain embodiments, it should be apparent that the method can beused to increase the viscosity of aqueous compositions that are alreadyviscous.

Contacting a poly alpha-1,3-glucan ether compound disclosed herein withan aqueous composition increases the viscosity of the aqueouscomposition in certain embodiments. This increase in viscosity can be anincrease of at least about 1%, 10%, 100%, 1000%, 100000%, or 1000000%(or any integer between 1% and 1000000%), for example, compared to theviscosity of the aqueous composition before the contacting step. Itshould be apparent that very large percent increases in viscosity can beobtained with the disclosed method when the aqueous composition haslittle to no viscosity before the contacting step.

Contacting a poly alpha-1,3-glucan ether compound disclosed herein withan aqueous composition increases the shear thinning behavior or theshear thickening behavior of the aqueous composition in certainembodiments. Thus, a poly alpha-1,3-glucan ether compound rheologicallymodifies the aqueous composition in these embodiments. The increase inshear thinning or shear thickening behavior can be an increase of atleast about 1%, 10%, 100%, 1000%, 100000%, or 1000000% (or any integerbetween 1% and 1000000%), for example, compared to the shear thinning orshear thickening behavior of the aqueous composition before thecontacting step. It should be apparent that very large percent increasesin rheologic modification can be obtained with the disclosed method whenthe aqueous composition has little to no rheologic behavior before thecontacting step.

The contacting step can be performed by mixing or dissolving a polyalpha-1,3-glucan ether compound(s) disclosed herein in the aqueouscomposition by any means known in the art. For example, mixing ordissolving can be performed manually or with a machine (e.g., industrialmixer or blender, orbital shaker, stir plate, homogenizer, sonicator,bead mill). Mixing or dissolving can comprise a homogenization step incertain embodiments. Homogenization (as well as any other type ofmixing) can be performed for about 5 to 60, 5 to 30, 10 to 60, 10 to 30,5 to 15, or 10 to 15 seconds (or any integer between 5 and 60 seconds),or longer periods of time as necessary to mix a poly alpha-1,3-glucanether compound with the aqueous composition. A homogenizer can be usedat about 5000 to 30000 rpm, 10000 to 30000 rpm, 15000 to 30000 rpm,15000 to 25000 rpm, or 20000 rpm (or any integer between 5000 and 30000rpm), for example. Hydrocolloids and aqueous solutions disclosed hereinprepared using a homogenization step can be termed as homogenizedhydrocolloids and aqueous solutions.

After a poly alpha-1,3-glucan ether compound is mixed with or dissolvedinto an aqueous composition, the resulting aqueous composition may befiltered, or may not be filtered. For example, an aqueous compositionprepared with a homogenization step may or may not be filtered.

Certain embodiments of the above method can be used to prepare anaqueous composition disclosed herein, such as a household product (e.g.,laundry detergent, fabric softener, dishwasher detergent), personal careproduct (e.g., a water-containing dentifrice such as toothpaste), orindustrial product.

The disclosed invention also concerns a method of treating a material.This method comprises contacting a material with an aqueous compositioncomprising at least one poly alpha-1,3-glucan ether compound disclosedherein. A poly alpha-1,3-glucan ether compound(s) used in this method isrepresented by the structure:

Regarding the formula of this structure, n can be at least 6, and each Rcan independently be an H or a positively charged organic group.Furthermore, the poly alpha-1,3-glucan ether compound has a degree ofsubstitution of about 0.05 to about 3.0.

A material contacted with an aqueous composition in a contacting methodherein can comprise a fabric in certain embodiments. A fabric herein cancomprise natural fibers, synthetic fibers, semi-synthetic fibers, or anycombination thereof. A semi-synthetic fiber herein is produced usingnaturally occurring material that has been chemically derivatized, anexample of which is rayon. Non-limiting examples of fabric types hereininclude fabrics made of (i) cellulosic fibers such as cotton (e.g.,broadcloth, canvas, chambray, chenille, chintz, corduroy, cretonne,damask, denim, flannel, gingham, jacquard, knit, matelassé, oxford,percale, poplin, plissé, sateen, seersucker, sheers, terry cloth, twill,velvet), rayon (e.g., viscose, modal, lyocell), linen, and Tencel®; (ii)proteinaceous fibers such as silk, wool and related mammalian fibers;(iii) synthetic fibers such as polyester, acrylic, nylon, and the like;(iv) long vegetable fibers from jute, flax, ramie, coir, kapok, sisal,henequen, abaca, hemp and sunn; and (v) any combination of a fabric of(i)-(iv). Fabric comprising a combination of fiber types (e.g., naturaland synthetic) include those with both a cotton fiber and polyester, forexample. Materials/articles containing one or more fabrics hereininclude, for example, clothing, curtains, drapes, upholstery, carpeting,bed linens, bath linens, tablecloths, sleeping bags, tents, carinteriors, etc. Other materials comprising natural and/or syntheticfibers include, for example, non-woven fabrics, paddings, paper, andfoams.

An aqueous composition that is contacted with a fabric can be, forexample, a fabric care composition (e.g., laundry detergent, fabricsoftener). Thus, a treatment method in certain embodiments can beconsidered a fabric care method or laundry method if employing a fabriccare composition therein. A fabric care composition herein can effectone or more of the following fabric care benefits (i.e., surfacesubstantive effects): wrinkle removal, wrinkle reduction, wrinkleresistance, fabric wear reduction, fabric wear resistance, fabricpilling reduction, fabric color maintenance, fabric color fadingreduction, fabric color restoration, fabric soiling reduction, fabricsoil release, fabric shape retention, fabric smoothness enhancement,anti-redeposition of soil on fabric, anti-greying of laundry, improvedfabric hand/handle, and/or fabric shrinkage reduction.

Examples of conditions (e.g., time, temperature, wash/rinse volumes) forconducting a fabric care method or laundry method herein are disclosedin WO1997/003161 and U.S. Pat. Nos. 4,794,661, 4,580,421 and 5,945,394,which are incorporated herein by reference. In other examples, amaterial comprising fabric can be contacted with an aqueous compositionherein: (i) for at least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90,100, 110, or 120 minutes; (ii) at a temperature of at least about 10,15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95°C. (e.g., for laundry wash or rinse: a “cold” temperature of about15-30° C., a “warm” temperature of about 30-50° C., a “hot” temperatureof about 50-95° C.); (iii) at a pH of about 2, 3, 4, 5, 6, 7, 8, 9, 10,11, or 12 (e.g., pH range of about 2-12, or about 3-11); (iv) at a salt(e.g., NaCl) concentration of at least about 0.5, 1.0, 1.5, 2.0, 2.5,3.0, 3.5, or 4.0 wt %; or any combination of (i)-(iv).

The contacting step in a fabric care method or laundry method cancomprise any of washing, soaking, and/or rinsing steps, for example.Contacting a material or fabric in still further embodiments can beperformed by any means known in the art, such as dissolving, mixing,shaking, spraying, treating, immersing, flushing, pouring on or in,combining, painting, coating, applying, affixing to, and/orcommunicating an effective amount of a poly alpha-1,3-glucan ethercompound herein with the fabric or material. In still furtherembodiments, contacting may be used to treat a fabric to provide asurface substantive effect. As used herein, the term “fabric hand” or“handle” refers to a person's tactile sensory response towards fabricwhich may be physical, physiological, psychological, social or anycombination thereof. In one embodiment, the fabric hand may be measuredusing a PhabrOmeter® System for measuring relative hand value (availablefrom Nu Cybertek, Inc. Davis, Calif.) (American Association of TextileChemists and Colorists (AATCC test method “202-2012, Relative Hand Valueof Textiles: Instrumental Method”)).

In certain embodiments of treating a material comprising fabric, a polyalpha-1,3-glucan ether compound component(s) of the aqueous compositionadsorbs to the fabric. This feature is believed to render polyalpha-1,3-glucan ether compounds (e.g., quaternary ammonium polyalpha-1,3-glucan ether compounds such as trimethylammonium hydroxypropylpoly alpha-1,3-glucan) useful as anti-redeposition agents and/oranti-greying agents in fabric care compositions disclosed herein (inaddition to their viscosity-modifying effect). An anti-redepositionagent or anti-greying agent herein helps keep soil from redepositingonto clothing in wash water after the soil has been removed. It isfurther contemplated that adsorption of one or more polyalpha-1,3-glucan ether compounds herein to a fabric enhances mechanicalproperties of the fabric.

The below Examples demonstrate that poly alpha-1,3-glucan ethercompounds such as quaternary ammonium poly alpha-1,3-glucan (e.g.,trimethylammonium hydroxypropyl poly alpha-1,3-glucan) can adsorb toboth natural (cotton, cretonne) and synthetic (polyester) fabrics, aswell as a blend thereof (polyester/cretonne). This result is notablegiven that carboxymethyl cellulose (CMC) does not absorb to, or onlypoorly adsorbs to, polyester and polyester/cotton blends (see EuropeanPat. Appl. Publ. No. EP0035478, for example). Thus, in certainembodiments of a treatment method herein, a cationic polyalpha-1,3-glucan ether compound (e.g., quaternary ammonium polyalpha-1,3-glucan such as trimethylammonium hydroxypropyl polyalpha-1,3-glucan) adsorbs to material comprising natural fiber (e.g.cotton) and/or synthetic fiber (e.g., polyester). Such adsorption mayoptionally be under conditions of about 1-2 wt % salt (e.g., NaCl),and/or a pH of about 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5,8.0, 8.5, 9.0, or 9.5, for example.

Adsorption of a poly alpha-1,3-glucan ether compound to a fabric hereincan be measured following the methodology disclosed in the belowExamples, for example. Alternatively, adsorption can be measured using acolorimetric technique (e.g., Dubois et al., 1956, Anal. Chem.28:350-356; Zemlji{hacek over (e)} et al., 2006, Lenzinger Berichte85:68-76; both incorporated herein by reference) or any other methodknown in the art.

Other materials that can be contacted in the above treatment methodinclude surfaces that can be treated with a dish detergent (e.g.,automatic dishwashing detergent or hand dish detergent). Examples ofsuch materials include surfaces of dishes, glasses, pots, pans, bakingdishes, utensils and flatware made from ceramic material, china, metal,glass, plastic (e.g., polyethylene, polypropylene, polystyrene, etc.)and wood (collectively referred to herein as “tableware”). Thus, thetreatment method in certain embodiments can be considered a dishwashingmethod or tableware washing method, for example. Examples of conditions(e.g., time, temperature, wash volume) for conducting a dishwashing ortableware washing method herein are disclosed in U.S. Pat. No.8,575,083, which is incorporated herein by reference. In other examples,a tableware article can be contacted with an aqueous composition hereinunder a suitable set of conditions such as any of those disclosed abovewith regard to contacting a fabric-comprising material.

Other materials that can be contacted in the above treatment methodinclude oral surfaces such as any soft or hard surface within the oralcavity including surfaces of the tongue, hard and soft palate, buccalmucosa, gums and dental surfaces (e.g., natural tooth or a hard surfaceof artificial dentition such as a crown, cap, filling, bridge, denture,or dental implant). Thus, a treatment method in certain embodiments canbe considered an oral care method or dental care method, for example.Conditions (e.g., time, temperature) for contacting an oral surface withan aqueous composition herein should be suitable for the intendedpurpose of making such contact. Other surfaces that can be contacted ina treatment method also include a surface of the integumentary systemsuch as skin, hair or nails.

Thus, certain embodiments of the disclosed invention concern material(e.g., fabric) that comprises a poly alpha-1,3-glucan ether compoundherein. Such material can be produced following a material treatmentmethod as disclosed, for example. A material may comprise a glucan ethercompound in certain embodiments if the compound is adsorbed to, orotherwise in contact with, the surface of the material.

Certain embodiments of a method of treating a material herein furthercomprise a drying step, in which a material is dried after beingcontacted with the aqueous composition. A drying step can be performeddirectly after the contacting step, or following one or more additionalsteps that might follow the contacting step (e.g., drying of a fabricafter being rinsed, in water for example, following a wash in an aqueouscomposition herein). Drying can be performed by any of several meansknown in the art, such as air drying (e.g., ˜20-25° C.), or at atemperature of at least about 30, 40, 50, 60, 70, 80, 90, 100, 120, 140,160, 170, 175, 180, or 200° C., for example. A material that has beendried herein typically has less than 3, 2, 1, 0.5, or 0.1 wt % watercomprised therein. Fabric is a preferred material for conducting anoptional drying step.

An aqueous composition used in a treatment method herein can be anyaqueous composition disclosed herein, such as in the above embodimentsor in the below Examples. Thus, the poly alpha-1,3-glucan ethercomponent(s) of an aqueous composition can be any as disclosed herein.Examples of aqueous compositions include detergents (e.g., laundrydetergent or dish detergent) and water-containing dentifrices such astoothpaste.

The disclosed invention also concerns a method for producing a polyalpha-1,3-glucan ether compound. This method comprises: contacting polyalpha-1,3-glucan in a reaction under alkaline conditions with at leastone etherification agent comprising a positively charged organic group,wherein the positively charged organic group is etherified to the polyalpha-1,3-glucan thereby producing a poly alpha-1,3-glucan ethercompound represented by the structure:

wherein(i) n is at least 6,(ii) each R is independently an H or the positively charged organicgroup, and(iii) the compound has a degree of substitution of about 0.05 to about3.0.A poly alpha-1,3-glucan ether produced by this method can optionally beisolated. This method can be considered to comprise an etherificationreaction.

Poly alpha-1,3-glucan is contacted in a reaction under alkalineconditions with at least one etherification agent comprising apositively charged organic group. This step can be performed, forexample, by first preparing alkaline conditions by contacting polyalpha-1,3-glucan with a solvent and one or more alkali hydroxides toprovide a solution or mixture. The alkaline conditions of the reactioncan thus comprise an alkali hydroxide solution. The pH of the alkalineconditions can be at least about 11.0, 11.2, 11.4, 11.6, 11.8, 12.0,12.2, 12.4, 12.6, 12.8, or 13.0.

Various alkali hydroxides can be used, such as sodium hydroxide,potassium hydroxide, calcium hydroxide, lithium hydroxide, and/ortetraethylammonium hydroxide. The concentration of alkali hydroxide in apreparation with poly alpha-1,3-glucan and a solvent can be from about1-70 wt %, 5-50 wt %, 10-50 wt %, 10-40 wt %, or 10-30 wt % (or anyinteger between 1 and 70 wt %). Alternatively, the concentration ofalkali hydroxide such as sodium hydroxide can be at least about 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, 29, or 30 wt %. An alkali hydroxide used toprepare alkaline conditions may be in a completely aqueous solution oran aqueous solution comprising one or more water-soluble organicsolvents such as ethanol or isopropanol. Alternatively, an alkalihydroxide can be added as a solid to provide alkaline conditions.

Various organic solvents that can optionally be included when preparingthe reaction include alcohols, acetone, dioxane, isopropanol andtoluene, for example; none of these solvents dissolve polyalpha-1,3-glucan. Toluene or isopropanol can be used in certainembodiments. An organic solvent can be added before or after addition ofalkali hydroxide. The concentration of an organic solvent (e.g.,isopropanol or toluene) in a preparation comprising polyalpha-1,3-glucan and an alkali hydroxide can be at least about 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 wt % (orany integer between 10 and 90 wt %).

Alternatively, solvents that can dissolve poly alpha-1,3-glucan can beused when preparing the reaction. These solvents include, but are notlimited to, lithium chloride (LiCl)/N,N-dimethyl-acetamide (DMAc),SO₂/diethylamine (DEA)/dimethyl sulfoxide (DMSO),LiCl/1,3-dimethy-2-imidazolidinone (DMI), N,N-dimethylformamide(DMF)/N₂O₄, DMSO/tetrabutyl-ammonium fluoride trihydrate (TBAF),N-methylmorpholine-N-oxide (NMMO), Ni(tren)(OH)₂[tren¼tris(2-aminoethyl)amine] aqueous solutions and melts ofLiClO₄.3H₂O, NaOH/urea aqueous solutions, aqueous sodium hydroxide,aqueous potassium hydroxide, formic acid, and ionic liquids.

Poly alpha-1,3-glucan can be contacted with a solvent and one or morealkali hydroxides by mixing. Such mixing can be performed during orafter adding these components with each other. Mixing can be performedby manual mixing, mixing using an overhead mixer, using a magnetic stirbar, or shaking, for example. In certain embodiments, polyalpha-1,3-glucan can first be mixed in water or an aqueous solutionbefore it is mixed with a solvent and/or alkali hydroxide.

After contacting poly alpha-1,3-glucan, solvent, and one or more alkalihydroxides with each other, the resulting composition can optionally bemaintained at ambient temperature for up to 14 days. The term “ambienttemperature” as used herein refers to a temperature between about 15-30°C. or 20-25° C. (or any integer between 15 and 30° C.). Alternatively,the composition can be heated with or without reflux at a temperaturefrom about 30° C. to about 150° C. (or any integer between 30 and 150°C.) for up to about 48 hours. The composition in certain embodiments canbe heated at about 55° C. for about 30 minutes or 60 minutes. Thus, acomposition obtained from mixing a poly alpha-1,3-glucan, solvent, andone or more alkali hydroxides with each other can be heated at about 50,51, 52, 53, 54, 55, 56, 57, 58, 59, or 60° C. for about 30-90 minutes.

After contacting poly alpha-1,3-glucan, solvent, and one or more alkalihydroxides with each other, the resulting composition can optionally befiltered (with or without applying a temperature treatment step). Suchfiltration can be performed using a funnel, centrifuge, press filter, orany other method and/or equipment known in the art that allows removalof liquids from solids. Though filtration would remove much of thealkali hydroxide, the filtered poly alpha-1,3-glucan would remainalkaline (i.e., mercerized poly alpha-1,3-glucan), thereby providingalkaline conditions.

An etherification agent comprising a positively charged organic groupcan be contacted with poly alpha-1,3-glucan in a reaction under alkalineconditions in a method herein of producing poly alpha-1,3-glucan ethercompounds. For example, an etherification agent can be added to acomposition prepared by contacting poly alpha-1,3-glucan, solvent, andone or more alkali hydroxides with each other as described above.Alternatively, an etherification agent can be included when preparingthe alkaline conditions (e.g., an etherification agent can be mixed withpoly alpha-1,3-glucan and solvent before mixing with alkali hydroxide).

An etherification agent herein refers to an agent that can be used toetherify one or more hydroxyl groups of the glucose units of polyalpha-1,3-glucan with a positively charged organic group as definedabove. One or more etherification agents may be used in the reaction.

An etherification agent may be one that can etherify polyalpha-1,3-glucan with a positively charged organic group, where thecarbon chain of the positively charged organic group only has asubstitution with a positively charged group (e.g., substituted ammoniumgroup such as trimethylammonium). Examples of such etherification agentsinclude dialkyl sulfates, dialkyl carbonates, alkyl halides (e.g., alkylchloride), iodoalkanes, alkyl triflates (alkyltrifluoromethanesulfonates) and alkyl fluorosulfonates, where the alkylgroup(s) of each of these agents has one or more substitutions with apositively charged group (e.g., substituted ammonium group such astrimethylammonium). Other examples of such etherification agents includedimethyl sulfate, dimethyl carbonate, methyl chloride, iodomethane,methyl triflate and methyl fluorosulfonate, where the methyl group(s) ofeach of these agents has a substitution with a positively charged group(e.g., substituted ammonium group such as trimethylammonium). Otherexamples of such etherification agents include diethyl sulfate, diethylcarbonate, ethyl chloride, iodoethane, ethyl triflate and ethylfluorosulfonate, where the ethyl group(s) of each of these agents has asubstitution with a positively charged group (e.g., substituted ammoniumgroup such as trimethylammonium). Other examples of such etherificationagents include dipropyl sulfate, dipropyl carbonate, propyl chloride,iodopropane, propyl triflate and propyl fluorosulfonate, where thepropyl group(s) of each of these agents has one or more substitutionswith a positively charged group (e.g., substituted ammonium group suchas trimethylammonium). Other examples of such etherification agentsinclude dibutyl sulfate, dibutyl carbonate, butyl chloride, iodobutaneand butyl triflate, where the butyl group(s) of each of these agents hasone or more substitutions with a positively charged group (e.g.,substituted ammonium group such as trimethylammonium).

An etherification agent may be one that can etherify polyalpha-1,3-glucan with a positively charged organic group, where thecarbon chain of the positively charged organic group has a substitution(e.g., hydroxyl group) in addition to a substitution with a positivelycharged group (e.g., substituted ammonium group such astrimethylammonium). Examples of such etherification agents includehydroxyalkyl halides (e.g., hydroxyalkyl chloride) such as hydroxypropylhalide and hydroxybutyl halide, where a terminal carbon of each of theseagents has a substitution with a positively charged group (e.g.,substituted ammonium group such as trimethylammonium); an example is3-chloro-2-hydroxypropyl-trimethylammonium. Other examples of suchetherification agents include alkylene oxides such as propylene oxide(e.g., 1,2-propylene oxide) and butylene oxide (e.g., 1,2-butyleneoxide; 2,3-butylene oxide), where a terminal carbon of each of theseagents has a substitution with a positively charged group (e.g.,substituted ammonium group such as trimethylammonium).

A substituted ammonium group comprised in any of the foregoingetherification agent examples can be a primary, secondary, tertiary, orquaternary ammonium group. Examples of secondary, tertiary andquaternary ammonium groups are represented in structure I, where R₂, R₃and R₄ each independently represent a hydrogen atom or an alkyl groupsuch as a methyl, ethyl, propyl, or butyl group.

Etherification agents herein typically can be provided as a fluoride,chloride, bromide, or iodide salt (where each of the foregoing halidesserve as an anion).

Any of the etherification agents disclosed herein may be combined toproduce poly alpha-1,3-glucan ether compounds with two or more differentpositively charged organic groups. Such two or more etherificationagents may be used in the reaction at the same time, or may be usedsequentially in the reaction. When used sequentially, any of thetemperature-treatment (e.g., heating) steps disclosed below mayoptionally be used between each addition. One may choose sequentialintroduction of etherification agents in order to control the desiredDoS of each positively charged organic group. In general, a particularetherification agent would be used first if the positively chargedorganic group it forms in the ether product is desired at a higher DoScompared to the DoS of another positively charged organic group to beadded.

The amount of etherification agent to be contacted with polyalpha-1,3-glucan in a reaction under alkaline conditions can bedetermined based on the degree of substitution required in the polyalpha-1,3-glucan ether compound being produced. The amount of ethersubstitution groups on each monomeric unit in poly alpha-1,3-glucanether compounds produced herein can be determined using nuclear magneticresonance (NMR) spectroscopy. The molar substitution (MS) value for polyalpha-1,3-glucan has no upper limit. In general, an etherification agentcan be used in a quantity of at least about 0.05 mole per mole of polyalpha-1,3-glucan. There is no upper limit to the quantity ofetherification agent that can be used.

Reactions for producing poly alpha-1,3-glucan ether compounds herein canoptionally be carried out in a pressure vessel such as a Parr reactor,an autoclave, a shaker tube or any other pressure vessel well known inthe art. A shaker tube is used to perform the reaction in certainembodiments.

A reaction herein can optionally be heated following the step ofcontacting poly alpha-1,3-glucan with an etherification agent underalkaline conditions. The reaction temperatures and time of applying suchtemperatures can be varied within wide limits. For example, a reactioncan optionally be maintained at ambient temperature for up to 14 days.Alternatively, a reaction can be heated, with or without reflux, betweenabout 25° C. to about 200° C. (or any integer between 25 and 200° C.).Reaction time can be varied correspondingly: more time at a lowtemperature and less time at a high temperature.

In certain embodiments of producing quaternary ammonium polyalpha-1,3-glucan ether (e.g., trimethylammonium hydroxypropyl polyalpha-1,3-glucan), a reaction can be heated to about 55° C. for about1.5 hours. Thus, a reaction for preparing a quaternary ammonium polyalpha-1,3-glucan ether such as trimethylammonium hydroxypropyl polyalpha-1,3-glucan can optionally be heated to about 50-60° C. for about1-2 hours, for example. Such a reaction may comprise3-chloro-2-hydroxypropyl-trimethylammonium as an etherification agent.

Optionally, a reaction herein can be maintained under an inert gas, withor without heating. As used herein, the term “inert gas” refers to a gaswhich does not undergo chemical reactions under a set of givenconditions, such as those disclosed for preparing a reaction herein.

All of the components of the reactions disclosed herein can be mixedtogether at the same time and brought to the desired reactiontemperature, whereupon the temperature is maintained with or withoutstirring until the desired poly alpha-1,3-glucan ether compound isformed. Alternatively, the mixed components can be left at ambienttemperature as described above.

Following etherification, the pH of a reaction can be neutralized.Neutralization of a reaction can be performed using one or more acids.The term “neutral pH” as used herein, refers to a pH that is neithersubstantially acidic or basic (e.g., a pH of about 6-8, or about 6.0,6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8, or 8.0). Various acids thatcan be used for this purpose include, but are not limited to, sulfuric,acetic, hydrochloric, nitric, any mineral (inorganic) acid, any organicacid, or any combination of these acids.

A poly alpha-1,3-glucan ether compound produced in a reaction herein canoptionally be washed one or more times with a liquid that does notreadily dissolve the compound. For example, poly alpha-1,3-glucan ethercan be washed with alcohol, acetone, aromatics, or any combination ofthese, depending on the solubility of the ether compound therein (wherelack of solubility is desirable for washing). A poly alpha-1,3-glucanether product can be washed one or more times with an aqueous solutioncontaining methanol or ethanol, for example. For example, 70-95 wt %ethanol can be used to wash the product. A poly alpha-1,3-glucan etherproduct can be washed with a methanol:acetone (e.g., 60:40) solution inanother embodiment.

A poly alpha-1,3-glucan ether produced in the disclosed reaction can beisolated. This step can be performed before or after neutralizationand/or washing steps using a funnel, centrifuge, press filter, or anyother method or equipment known in the art that allows removal ofliquids from solids. For example, a Buchner funnel may be used toisolate a poly alpha-1,3-glucan ether product. An isolated polyalpha-1,3-glucan ether product can be dried using any method known inthe art, such as vacuum drying, air drying, or freeze drying.

Any of the above etherification reactions can be repeated using a polyalpha-1,3-glucan ether product as the starting material for furthermodification. This approach may be suitable for increasing the DoS of apositively charged organic group, and/or adding one or more differentpositively charged organic groups to the ether product. Also, thisapproach may be suitable for adding one or more organic groups that arenot positively charged, such as an alkyl group (e.g., methyl, ethyl,propyl, butyl) and/or a hydroxyalkyl group (e.g., hydroxyethyl,hydroxypropyl, hydroxybutyl). Any of the above etherification agents,but without the substitution with a positively charged group, can beused for this purpose.

The structure, molecular weight and degree of substitution of a polyalpha-1,3-glucan ether product can be confirmed using variousphysiochemical analyses known in the art such as NMR spectroscopy andsize exclusion chromatography (SEC).

The percentage of glycosidic linkages between the glucose monomer unitsof poly alpha-1,3-glucan used to prepare poly alpha-1,3-glucan ethercompounds herein that are alpha-1,3 is at least about 50%, 60%, 70%,80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% (or any integer value between50% and 100%). In such embodiments, accordingly, poly alpha-1,3-glucanhas less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1%, or 0%(or any integer value between 0% and 50%) of glycosidic linkages thatare not alpha-1,3.

Poly alpha-1,3-glucan used to prepare poly alpha-1,3-glucan ethercompounds herein is preferably linear/unbranched. In certainembodiments, poly alpha-1,3-glucan has no branch points or less thanabout 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% branch points as apercent of the glycosidic linkages in the polymer. Examples of branchpoints include alpha-1,6 branch points.

The M_(n) or M_(w) of poly alpha-1,3-glucan used to prepare polyalpha-1,3-glucan ether compounds herein may be at least about 1000 toabout 600000. Alternatively still, M_(n) or M_(w) can be at least about2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 20000,25000, 30000, 35000, 40000, 45000, 50000, 75000, 100000, 150000, 200000,250000, 300000, 350000, 400000, 450000, 500000, 550000, or 600000 (orany integer between 2000 and 600000), for example.

Poly alpha-1,3-glucan used for preparing poly alpha-1,3-glucan ethercompounds herein can be enzymatically produced from sucrose using one ormore glucosyltransferase (gtf) enzymes. The poly alpha-1,3-glucanproduct of this enzymatic reaction can be purified before using it toprepare an ether using the disclosed process. Alternatively, a polyalpha-1,3-glucan product of a gtf reaction can be used with little or noprocessing for preparing poly alpha-1,3-glucan ether compounds.

A poly alpha-1,3-glucan slurry can be used directly in any of the aboveprocesses for producing a poly alpha-1,3-glucan ether compound disclosedherein. As used herein, a “poly alpha-1,3-glucan slurry” refers to amixture comprising the components of a gtf enzymatic reaction. A gtfenzymatic reaction can include, in addition to poly alpha-1,3-glucanitself, various components such as sucrose, one or more gtf enzymes,glucose, fructose, leucrose, buffer, FermaSure®, solubleoligosaccharides, oligosaccharide primers, bacterial enzyme extractcomponents, borates, sodium hydroxide, hydrochloric acid, cell lysate,proteins and/or nucleic acids. Minimally, the components of a gtfenzymatic reaction can include, in addition to poly alpha-1,3-glucanitself, sucrose, one or more gtf enzymes, glucose and fructose, forexample. In another example, the components of a gtf enzymatic reactioncan include, in addition to poly alpha-1,3-glucan itself, sucrose, oneor more gtf enzymes, glucose, fructose, leucrose and solubleoligosaccharides (and optionally bacterial enzyme extract components).It should be apparent that poly alpha-1,3-glucan, when in a slurry asdisclosed herein, has not been purified or washed. It should also beapparent that a slurry represents a gtf enzymatic reaction that iscomplete or for which an observable amount of poly alpha-1,3-glucan hasbeen produced, which forms a solid since it is insoluble in the aqueousreaction milieu (has pH of 5-7, for example). A poly alpha-1,3-glucanslurry can be prepared by setting up a gtf reaction as disclosed in U.S.Pat. No. 7,000,000 or U.S. Patent Appl. Publ. Nos. 2013/0244288 and2013/0244287, for example, all of which are incorporated herein byreference. A poly alpha-1,3-glucan slurry can be entered into a reactionfor producing any ether compound herein, such as a quaternary ammoniumpoly alpha-1,3-glucan ether (e.g., trimethylammonium hydroxypropyl polyalpha-1,3-glucan).

Alternatively, a wet cake of poly alpha-1,3-glucan can be used directlyin any of the above processes for producing a poly alpha-1,3-glucanether compound disclosed herein. A “wet cake of poly alpha-1,3-glucan”as used herein refers to poly alpha-1,3-glucan that has been separated(e.g., filtered) from a slurry and washed with water or an aqueoussolution. A wet cake can be washed at least 1, 2, 3, 4, 5, or moretimes, for example. The poly alpha-1,3-glucan is not dried whenpreparing a wet cake. A wet cake is termed as “wet” given the retentionof water by the washed poly alpha-1,3-glucan.

A wet cake of poly alpha-1,3-glucan can be prepared using any deviceknown in the art for separating solids from liquids, such as a filter orcentrifuge. For example, poly alpha-1,3-glucan solids in a slurry can becollected on a Buchner funnel using a mesh screen over filter paper.Filtered wet cake can be resuspended in water (e.g., deionized water)and filtered one or more times to remove soluble components of theslurry such as sucrose, fructose and leucrose. As another example forpreparing a wet cake, poly alpha-1,3-glucan solids from a slurry can becollected as a pellet via centrifugation, resuspended in water (e.g.,deionized water), and re-pelleted and resuspended one or more additionaltimes. A poly alpha-1,3-glucan wet cake can be entered into a reactionfor producing any ether compound herein, such as a quaternary ammoniumpoly alpha-1,3-glucan ether (e.g., trimethylammonium hydroxypropyl polyalpha-1,3-glucan).

Poly alpha-1,3-glucan ether compounds disclosed herein may becrosslinked using any means known in the art. Such crosslinkage may bebetween the same poly alpha-1,3-glucan ether compounds, or between twoor more different poly alpha-1,3-glucan ether compounds. Also,crosslinkage may be intermolecular and/or intramolecular.

A crosslinked poly alpha-1,3-glucan ether compound can be prepared asfollows, for example. One or more poly alpha-1,3-glucan ether compoundscan be dissolved in water or an aqueous solution to prepare a 0.2, 0.5,1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt % solution of the ether compound(s).Poly alpha-1,3-glucan ether compound(s) can be dissolved or mixed usingany process known in the art, such as by increasing temperature, manualmixing, and/or homogenization (as described above).

A crosslinking agent is next dissolved in the poly alpha-1,3-glucanether solution or mixture. The concentration of the crosslinking agentin the resulting solution can be about 0.2 to 20 wt %, or about 0.1,0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 wt %.

Examples of suitable crosslinking agents are boron-containing compoundsand polyvalent metals such as titanium or zirconium. Boron-containingcompounds include boric acid, diborates, tetraborates, pentaborates,polymeric compounds such as Polybor®, polymeric compounds of boric acid,and alkali borates, for example. These agents can be used to produceborate crosslinks between poly alpha-1,3-glucan ether molecules.Titanium crosslinks may be produced using titanium IV-containingcompounds (e.g., titanium ammonium lactate, titanium triethanolamine,titanium acetylacetonate, polyhydroxy complexes of titanium) ascrosslinking agents. Zirconium crosslinks can be produced usingzirconium IV-containing compounds (e.g., zirconium lactate, zirconiumcarbonate, zirconium acetylacetonate, zirconium triethanolamine,zirconium diisopropylamine lactate, polyhydroxy complexes of zirconium)as crosslinking agents. Other examples of crosslinking agents usefulherein are described in U.S. Pat. Nos. 4,462,917, 4,464,270, 4,477,360and 4,799,550, which are all incorporated herein by reference.

The pH of the solution or mixture containing both a crosslinkingagent(s) and a poly alpha-1,3-glucan ether compound(s) can be adjustedto be alkali (e.g., pH of 8, 8.5, 9, 9.5, or 10). Modification of pH canbe done by any means known in the art, such as with a concentratedaqueous solution of an alkali hydroxide such as sodium hydroxide.Dissolving a crosslinking agent in a solution or mixture containing oneor more poly alpha-1,3-glucan ether compounds at an alkali pH results incrosslinking of the poly alpha-1,3-glucan ether compound(s).

EXAMPLES

The disclosed invention is further defined in the following Examples. Itshould be understood that these Examples, while indicating certainpreferred aspects of the invention, are given by way of illustrationonly. From the above discussion and these Examples, one skilled in theart can ascertain the essential characteristics of this invention, andwithout departing from the spirit and scope thereof, can make variouschanges and modifications of the invention to adapt it to various usesand conditions.

Preparation of Poly Alpha-1,3-Glucan

Poly alpha-1,3-glucan was prepared using a gtfJ enzyme preparation asdescribed in U.S. Patent Appl. Publ. No. 2013/0244288, which isincorporated herein by reference in its entirety.

¹H Nuclear Magnetic Resonance (NMR) Method for Determining MolarSubstitution of Poly Alpha-1,3-Glucan Ether Derivatives

Approximately 30 mg of the poly alpha-1,3-glucan ether derivative wasweighed into a vial on an analytical balance. The vial was removed fromthe balance and 1.0 mL of deuterium oxide was added to the vial. Amagnetic stir bar was added to the vial and the mixture was stirred tosuspend the solid. Deuterated sulfuric acid (50% v/v in D₂O), 1.0 mL,was then added to the vial and the mixture was heated at 90° C. for 1hour in order to depolymerize and solubilize the polymer. The solutionwas allowed to cool to room temperature and then a 0.8 mL portion of thesolution was transferred into a 5-mm NMR tube using a glass pipet. Aquantitative ¹H NMR spectrum was acquired using an Agilent VNMRS 400 MHzNMR spectrometer equipped with a 5-mm Autoswitchable Quad probe. Thespectrum was acquired at a spectral frequency of 399.945 MHz, using aspectral window of 6410.3 Hz, an acquisition time of 3.744 seconds, aninter-pulse delay of 10 seconds and 64 pulses. The time domain data weretransformed using exponential multiplication of 0.50 Hz.

Determination of Degree of Polymerization

Degree of polymerization (DP) was determined by size exclusionchromatography (SEC). For SEC analysis, dry poly alpha-1,3-glucan etherderivative was dissolved in phosphate-buffered saline (PBS) (0.02-0.2mg/mL). The chromatographic system used was an Alliance™ 2695 liquidchromatograph from Waters Corporation (Milford, Mass.) coupled withthree on-line detectors: a differential refractometer 410 from Waters, amulti-angle light-scattering photometer Heleos™ 8+ from WyattTechnologies (Santa Barbara, Calif.), and a differential capillaryviscometer ViscoStar™ from Wyatt Technologies. The columns used for SECwere two Tosoh Haas Bioscience TSK GMPW_(XL)g3K and g4K G3000PW andG4000PW polymeric columns for aqueous polymers. The mobile phase wasPBS. The chromatographic conditions used were 30° C. at column anddetector compartments, 30° C. at sample and injector compartments, aflow rate of 0.5 mL/min, and injection volume of 100 μL. The softwarepackages used for data reduction were Astra version 6 from Wyatt (tripledetection method with column calibration).

Homogenization

Homogenization was performed using an IKA ULTRA TURRAX T25 DigitalHomogenizer (IKA, Wilmington, N.C.).

Example 1 Preparation of Quaternary Ammonium Poly Alpha-1,3-Glucan

This Example describes producing a quaternary ammonium polyalpha-1,3-glucan ether derivative. Specifically, trimethylammoniumhydroxypropyl poly alpha-1,3-glucan was produced.

10 g of poly alpha-1,3-glucan (M_(w) [weight-average molecularweight]=168,000) was added to 100 mL of isopropanol in a 500-mL capacityround bottom flask fitted with a thermocouple for temperature monitoringand a condenser connected to a recirculating bath, and a magnetic stirbar. 30 mL of sodium hydroxide (17.5% solution) was added dropwise tothis preparation, which was then heated to 25° C. on a hotplate. Thepreparation was stirred for 1 hour before the temperature was increasedto 55° C. 3-chloro-2-hydroxypropyl-trimethylammonium chloride (31.25 g)was then added to provide a reaction, which was held at 55° C. for 1.5hours before being neutralized with 90% acetic acid. The solid thusformed (trimethylammonium hydroxypropyl poly alpha-1,3-glucan) wascollected by vacuum filtration and washed with ethanol (95%) four times,dried under vacuum at 20-25° C., and analyzed by NMR and SEC todetermine molecular weight and DoS.

Additional samples of trimethylammonium hydroxypropyl polyalpha-1,3-glucan were synthesized following the above process, but withcertain process variations. Specifically, poly alpha-1,3-glucan sampleswith various M_(w)'s were used as starting material, and differentamounts of etherification agent(3-chloro-2-hydroxypropyl-trimethylammonium chloride) were used. Also,reaction time (beginning from addition of etherification agent andending at neutralization) was varied. Table 1 lists these variousprocess variations and the resulting DoS measurements of the quaternaryammonium glucan ether products.

TABLE 1 DoS of Quaternary Ammonium Hydroxypropyl Poly Alpha-1,3-GlucanPrepared from Poly Alpha-1,3-Glucan M_(w) of poly alpha-1,3- glucanEtherification Reaction Sample starting Agent Time Designation materialAmount (hours) ^(a) DoS 1A 99231 31.25 g 3 1.26 1B-1 99231 31.25 g 10.59 1B-2 2 1.05 1B-3 4 1.29 1C-1 99231 9 g 1 0.39 1C-2 2 0.35 1C-3 40.31 1D 168000 15 g 2.5 0.43 1E-1 189558 18 g 1 0.34 1E-2 2 0.37 1E-3 40.45 1F 247182 31.25 g 4 0.17 1G 163200 31.25 g 3 0.52 1F 34083 31.25 g2.5 1.19 ^(a) Reaction time was measured from the time etherificationagent was added to the time of reaction neutralization.

Thus, the quaternary ammonium glucan ether derivative, trimethylammoniumhydroxypropyl poly alpha-1,3-glucan, was prepared and isolated.

Example 2 Effect of Shear Rate on Viscosity of Quaternary Ammonium PolyAlpha-1,3-Glucan

This Example describes the effect of shear rate on the viscosity oftrimethylammonium hydroxypropyl poly alpha-1,3-glucan. It is shown thatthis glucan ether derivative exhibits shear thinning behavior. Thus,addition of trimethylammonium hydroxypropyl poly alpha-1,3-glucan to aliquid can modify the rheological behavior of the liquid.

Various samples of trimethylammonium hydroxypropyl poly alpha-1,3-glucanwere prepared as described in Example 1. To prepare a 2 wt % solution ofeach sample, 1 g of sample was added to 49 g of DI water. Eachpreparation was then homogenized for 12-15 seconds at 20,000 rpm todissolve the trimethylammonium hydroxypropyl poly alpha-1,3-glucansample in the water.

To determine the viscosity of each 2 wt % quaternary ammonium glucansolution at various shear rates, each solution was subjected to variousshear rates using a Brookfield DV III+Rheometer equipped with arecirculating bath to control temperature (20° C.) and a ULA (ultra lowadapter) spindle and adapter set. The shear rate was increased using agradient program which increased from 10-250 rpm and the shear rate wasincreased by 4.9 1/s every 20 seconds for the ULA spindle and adapter.The results of the experiment are listed in Table 2.

TABLE 2 Viscosity of Quaternary Ammonium Hydroxypropyl PolyAlpha-1,3-Glucan Solutions at Various Shear Rates Viscosity ViscosityViscosity Viscosity (cPs) @ (cPs) @ (cPs) @ (cPs) @ Sample^(a) 66.18 rpm102.9 rpm 183.8 rpm 250 rpm 1A 26.26 24.95 23.42 22.6 1B-1 98.87 83.2270.27 64.43 1B-2 43.76 41.53 38.24 36.57 1B-3 21.53 20.08 19.16 18.721C-1 225.81 158.76 102.02 85.6 1C-2 1246.67 810.93 436.29 334.8 1C-31601.44 992.24 563.95 421.2 1E-1 739.62 493.41 269.67 224 ^(a)Eachsample is described in Table 1.

The results summarized in Table 2 indicate that the viscosity of each ofthe quaternary ammonium poly alpha-1,3-glucan solutions is reduced asthe shear rate is increased. This observation means that these solutionsdemonstrate shear thinning behavior.

Thus, trimethylammonium hydroxypropyl poly alpha-1,3-glucan whendissolved in an aqueous solution not only modifies the viscosity of thesolution, but also the rheological properties of the solution. Thisquaternary ammonium glucan can therefore be added to an aqueous liquidto modify its rheological profile.

Example 3 Creating Calibration Curve for Direct Red 80 Dye Using UVAbsorption

This example discloses creating a calibration curve useful fordetermining the relative level of adsorption of poly alpha-1,3-glucanether derivatives onto fabric surfaces.

Solutions of known concentration (ppm) were made using Direct Red 80dye. The absorbance of these solutions was measured using a LAMOTTESMART2 Colorimeter at either 520 or 620 nm. The absorption informationwas plotted in order that it could be used to determine dyeconcentration of solutions which were exposed to fabric samples. Theconcentration and absorbance of each calibration curve are provided inTable 3.

TABLE 3 Direct Red 80 Dye Calibration Curve Data Dye AverageConcentration Absorbance (ppm) @520 nm 25 0.823333333 22.5 0.79666666720 0.666666667 15 0.51 10 0.37 5 0.2

Thus, a calibration curve was prepared that is useful for determiningthe relative level of adsorption of poly alpha-1,3-glucan etherderivatives onto fabric surfaces. This calibration curve was utilized inExample 4.

Example 4 Adsorption of Quaternary Ammonium Poly Alpha-1,3-Glucan Etheron Various Fabrics

This example discloses testing the degree of adsorption of a quaternaryammonium poly alpha-1,3-glucan (trimethylammonium hydroxypropyl polyalpha-1,3-glucan) on different types of fabrics.

A 0.07 wt % solution of trimethylammonium hydroxypropyl polyalpha-1,3-glucan (Sample 1F, Table 1) was made by dissolving 0.105 g ofthe polymer in 149.89 g of deionized water. This solution was dividedinto several aliquots with different concentrations of polymer and othercomponents (Table 4). Such other components were acid (dilutehydrochloric acid) or base (sodium hydroxide) to modify pH, or NaClsalt.

TABLE 4 Quaternary Ammonium Poly Alpha-1,3-Glucan Solutions Used inFabric Adsorption Studies Amount Amount Polymer Amount Amount of NaCl ofSolution Concentration of Acid of Base Final (g) (g) (wt %) (g) (g) pH 015 0.07 n/a n/a ~7 0.15 14.85 0.0693 n/a n/a ~7 0.3 14.7 0.0686 n/a n/a~7 0.45 14.55 0.0679 n/a n/a ~7 0 9.7713 0.0683 0.2783 n/a 2.92 0 9.77240.0684 0.2369 n/a 4.96 0 10.0311 0.0702 n/a 0.0319 9.04 0 9.9057 0.0693n/a 0.1059 11.05

Four different fabric types (cretonne, polyester, 65:35polyester/cretonne, bleached cotton) were cut into 0.17 g pieces. Eachpiece was placed in a 2-mL well in a 48-well cell culture plate. Eachfabric sample was exposed to 1 mL of each of the above solutions (Table4) for a total of 36 samples (a control solution with no polymer wasincluded for each fabric test). The fabric samples were allowed to sitfor at least 30 minutes in the polymer solutions. The fabric sampleswere removed from the polymer solutions and rinsed in DI water for atleast one minute to remove any unbound polymer. The fabric samples werethen dried at 60° C. for at least 30 minutes until constant dryness wasachieved. The fabric samples were weighed after drying and individuallyplaced in 2-mL wells in a clean 48-well cell culture plate. The fabricsamples were then exposed to 1 mL of a 250 ppm Direct Red 80 dyesolution. The samples were left in the dye solution for at least 15minutes. Each fabric sample was removed from the dye solution,afterwhich the dye solution was diluted 10×.

The absorbance of the diluted solutions was measured compared to acontrol sample. A relative measure of glucan polymer adsorbed to thefabric was calculated based on the calibration curve created in Example3 for Direct Red 80 dye. Specifically, the difference in UV absorbancefor the fabric samples exposed to polymer compared to the controls(fabric not exposed to polymer) represents a relative measure of polymeradsorbed to the fabric. This difference in UV absorbance could also beexpressed as the amount of dye bound to the fabric (over the amount ofdye bound to control), which was calculated using the calibration curve(i.e., UV absorbance was converted to ppm dye). Table 5 provides “dye(ppm)”; a positive value represents the dye amount that was in excess tothe dye amount bound to the control fabric, whereas a negative valuerepresents the dye amount that was less than the dye amount bound to thecontrol fabric. A positive value reflects that the glucan ether compoundadsorbed to the fabric surface.

TABLE 5 Relative Amount of Quaternary Ammonium Poly Alpha-1,3-GlucanBound to Different Fabrics Under Different Conditions 65:35 Polyester/Bleached Cretonne Polyester Cretonne Cotton Salt dye Salt dye Salt dyeSalt dye Conc. (ppm)^(a) Conc. (ppm)^(a) Conc. (ppm)^(a) Conc. (ppm)^(a) 0^(b) +4.56  0^(b) +0.48  0^(b) +1.27  0^(b) +3.13 1%^(b) +1.97 1%^(b)+0.46 1%^(b) +0.58 1%^(b) +3.78 2%^(b) −0.52 2%^(b) +0.0003 2%^(b) +0.162%^(b) +4.11 3%^(b) 0 3%^(b) +0.10 3%^(b) +0.07 3%^(b) −0.13 pH^(c)pH^(c) pH^(c) pH^(c) 3 +2.06 3 −0.29 3 −0.26 3 +2.97 5 +3.13 5 +0.13 5−0.33 5 +2.87 9 +2.05 9 −0.003 9 +0.07 9 +4.69 11  +2.02 11  −0.59 11 +0.12 11  +2.03 ^(a)Amount of dye bound to fabric. A positive valuerepresents the dye amount that was in excess to the dye amount bound tocontrol. A positive dye amount in turn represents the relative amount ofglucan ether adsorbed to the fabric. ^(b)The pH of binding conditionswas about 7 (refer to Table 4). ^(c)Binding conditions did not includesalt (refer to Table 4).

The data in Table 5 indicate that quaternary ammonium glucan polymer canadsorb to various types of fabric under different salt and pHconditions. This adsorption occurs even though the fabrics were rinsedafter exposure to the polymer. It is notable that the glucan ether wasable to adsorb to polyester and the polyester/cretonne blend, inaddition to adsorbing to cotton.

Thus, a poly alpha-1,3-glucan ether derivative in an aqueous compositioncan adsorb to fabric.

What is claimed is:
 1. A composition comprising a poly alpha-1,3-glucanether compound represented by the structure:

wherein (i) n is at least 6, (ii) each R is independently an H or apositively charged organic group, and (iii) the compound has a degree ofsubstitution of about 0.05 to about 3.0.
 2. The composition of claim 1,wherein at least one positively charged organic group comprises asubstituted ammonium group.
 3. The composition of claim 2, wherein thepositively charged organic group comprises a trimethylammonium group. 4.The composition of claim 2, wherein the positively charged organic groupis a quaternary ammonium group.
 5. The composition of claim 1, whereinat least one positively charged organic group comprises an alkyl groupor hydroxy alkyl group.
 6. The composition of claim 5, wherein at leastone positively charged organic group is a quaternary ammoniumhydroxypropyl group.
 7. A method of producing a poly alpha-1,3-glucanether compound, the method comprising: (a) contacting polyalpha-1,3-glucan in a reaction under alkaline conditions with at leastone etherification agent comprising a positively charged organic group,wherein at least one positively charged organic group is etherified tothe poly alpha-1,3-glucan thereby producing a poly alpha-1,3-glucanether compound represented by the structure:

wherein (i) n is at least 6, (ii) each R is independently an H or thepositively charged organic group, and (iii) the compound has a degree ofsubstitution of about 0.05 to about 3.0; and (b) optionally, isolatingthe poly alpha-1,3-glucan ether compound produced in step (a).
 8. Themethod of claim 7, wherein said alkaline conditions comprise an alkalihydroxide solution.
 9. The method of claim 7, wherein the reactioncomprises an organic solvent.
 10. The method of claim 9, wherein theorganic solvent is isopropanol.
 11. The method of claim 7, wherein step(a) further comprises: (i) heating the reaction; and/or (ii)neutralizing the pH of the reaction.
 12. The method of claim 7, whereinat least one positively charged organic group comprises a substitutedammonium group.
 13. The method of claim 12, wherein at least onepositively charged organic group comprises a trimethylammonium group.14. A hydrocolloid or aqueous solution comprising a polyalpha-1,3-glucan ether compound represented by the structure:

wherein (i) n is at least 6, (ii) each R is independently an H or apositively charged organic group, (iii) the compound has a degree ofsubstitution of about 0.05 to about 3.0, and (iv) the hydrocolloid oraqueous solution has a viscosity of at least about 10 cPs.
 15. A methodfor increasing the viscosity of an aqueous composition, the methodcomprising: contacting a poly alpha-1,3-glucan ether compound with theaqueous composition, wherein the viscosity of the aqueous composition isincreased by said compound, wherein said compound is represented by thestructure:

wherein (i) n is at least 6, (ii) each R is independently an H or apositively charged organic group, and (iii) the compound has a degree ofsubstitution of about 0.05 to about 3.0.
 16. A method of treating amaterial, said method comprising: contacting a material with an aqueouscomposition comprising a poly alpha-1,3-glucan ether compoundrepresented by the structure:

wherein (i) n is at least 6, (ii) each R is independently an H or apositively charged organic group, and (iii) the compound has a degree ofsubstitution of about 0.05 to about 3.0.